JP3964326B2 - Carboxyl group-containing photosensitive resin, alkali-developable photocurable / thermosetting composition containing the same, and cured product thereof - Google Patents

Carboxyl group-containing photosensitive resin, alkali-developable photocurable / thermosetting composition containing the same, and cured product thereof Download PDF

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JP3964326B2
JP3964326B2 JP2002529182A JP2002529182A JP3964326B2 JP 3964326 B2 JP3964326 B2 JP 3964326B2 JP 2002529182 A JP2002529182 A JP 2002529182A JP 2002529182 A JP2002529182 A JP 2002529182A JP 3964326 B2 JP3964326 B2 JP 3964326B2
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photosensitive resin
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登 小檜山
滋 宇敷
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Taiyo Ink Manufacturing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

Description

技術分野
本発明は、ノボラック型フェノール樹脂のアルキレンオキシドの付加反応による鎖延長、それに続くアクリル酸及び／又はメタクリル酸の付加及び多塩基酸無水物の付加によって得られる光及び／又は熱硬化性樹脂に関し、さらに詳しくは、その硬化物が耐熱性、強靱性に優れると共に、高い硬度と可撓性を有し、しかも耐水性、耐薬品性に富んだ光及び／又は熱硬化性樹脂に関する。
さらに本発明は、アルカリ現像可能な光硬化性・熱硬化性組成物及びそれから得られる硬化物に関し、さらに詳しくは、一般のプリント配線板や、フレキシブルプリント配線板、テープキャリアパッケージの製造に用いられる永久マスクや、多層配線板の層間絶縁層等としての使用に適し、紫外線の照射後、希アルカリ水溶液で現像することによって画像形成し、加熱処理、又は活性エネルギー線照射後の加熱処理、もしくは加熱処理後の活性エネルギー線照射により仕上げ硬化することにより、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ（プレッシャークッカー）耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性に優れる硬化膜を形成できる液状のアルカリ現像可能な光硬化性・熱硬化性組成物並びにその硬化膜に関する。
背景技術
現在、一部の民生用プリント配線板並びにほとんどの産業用プリント配線板用ソルダーレジストには、高精度、高密度の観点から、紫外線照射後、現像することにより画像形成し、熱又は光照射で仕上げ硬化（本硬化）する液状現像型ソルダーレジストが使用されている。また環境問題への配慮から、現像液として希アルカリ水溶液を用いるアルカリ現像タイプの液状ソルダーレジストが主流になっている。このような希アルカリ水溶液を用いるアルカリ現像タイプのソルダーレジストとしては、例えば、特開昭６１−２４３８６９号公報には、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤及びエポキシ化合物からなるソルダーレジスト組成物が、特開平３−２５３０９３号公報には、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤、ビニルトリアジン又はビニルトリアジンとジシアンジアミドの混合物及びメラミン樹脂からなるソルダーレジスト組成物が、特開平３−７１１３７号公報、特開平３−２５００１２号公報には、サリチルアルデヒドと一価フェノールとの反応生成物にエピクロロヒドリンを反応させて得られたエポキシ樹脂に（メタ）アクリル酸を付加し、さらに多塩基性カルボン酸又はその無水物を反応させて得られる感光性樹脂、光重合開始剤、有機溶剤等からなるソルダーレジスト組成物が開示されている。
上記のように、ソルダーレジストとしては従来幾つかの材料系が提案されており、現在、実際のプリント配線板の製造において大量に使用されている。しかしながら、近年のエレクトロニクス機器の軽薄短小化に伴うプリント配線板の高密度化に対応して、ソルダーレジストにも高性能化が要求されている。さらに最近では、リードフレームと封止樹脂を用いたＱＦＰ（クワッド・フラットパック・パッケージ）やＳＯＰ（スモール・アウトライン・パッケージ）等と呼ばれるＩＣパッケージに代わって、ソルダーレジストを施したプリント配線板と封止樹脂を用いたＩＣパッケージが登場した。これら新しいパッケージは、ソルダーレジストを施したプリント配線板の片側にボール状のはんだ等の金属をエリア状に配し、もう片側にＩＣチップをワイヤーボンディングもしくはバンプ等で直接接続し、封止樹脂で封止した構造をしており、ＢＧＡ（ボール・グリッド・アレイ）、ＣＳＰ（チップ・スケール・パッケージ）等の呼び名で呼ばれている。これらのパッケージは、同一サイズのＱＦＰ等のパッケージよりも多ピンでさらに小型化が容易である。また実装においても、ボール状はんだのセルフアライメント効果により低い不良率を実現し、急速にその導入が進められている。
しかしながら、従来市販のアルカリ現像型ソルダーレジストを施したプリント配線板では、パッケージの長期信頼性試験であるＰＣＴ耐性が劣り、硬化物の剥離が生じている。また、ソルダーレジストの吸湿により、パッケージ実装時のリフロー中にパッケージ内部で吸湿した水分が沸騰し、パッケージ内部のソルダーレジスト皮膜及びその周辺にクラックが生じる、いわゆるポップコーン現象が問題視されている。このような耐吸湿性や長期信頼性の問題は、上記実装技術の場合のみに限られるものではなく、一般のプリント配線板のソルダーレジストや、フレキシブルプリント配線板やテープキャリアパッケージの製造に用いられるソルダーレジストや、ビルドアップ基板等の多層配線板の層間絶縁層など、他の用途の製品においても望ましくない。
このように、最近の電気産業、半導体産業の発展に伴って、一層の特性向上、例えば、耐熱性、強靱性、可撓性、耐水性、耐薬品性の向上が要求され、これを満足すべく種々の新規な感光性樹脂が開発されている。
従来、ノボラック型エポキシ樹脂を出発原料とした感光性樹脂は、その優れた接着性、耐熱性、耐薬品性、電気絶縁性などのため、ソルダーレジスト、エッチングレジストなど電子材料の多くの分野に広く使用されており、特に耐熱性の優れたカルボキシル基含有感光性樹脂として、前記クレゾールノボラック型エポキシ樹脂と不飽和基含有モノカルボン酸との反応生成物に多塩基酸無水物を反応させて得られる樹脂（特開昭６１−２４３８６９号）が多用されている。しかし、この樹脂は耐熱性に優れるものの、硬化時の収縮が大きく、伸びが少なく、強靱性に欠けるため、熱ショックによるクラックが発生し易いという難点がある。
これを解決する感光性樹脂として、ビスフェノール型エポキシ樹脂の側鎖水酸基を部分エポキシ化した樹脂と（メタ）アクリル酸と多塩基酸無水物との反応生成物である感光性プレポリマー（特開平９−５４４３４号）、クレゾールノボラック型エポキシ樹脂とアクリル酸とｐ−ヒドロキシフェネチルアルコールの反応生成物にテトラヒドロフタル酸無水物を反応させて得られる不飽和基含有ポリカルボン酸樹脂（特開平１１−２８８０９１号）などが提案されている。
しかし、これらの樹脂も、耐熱性と強靭性を共に満足させるにはまだまだ不充分である。
本発明は、前記の様な問題に鑑みなされたものであり、バランスのとれた耐熱性と強靭性に加え、良好な伸び、耐水性、耐薬品性等を有し、かつ良好な可撓性を持つ硬化物が得られるカルボキシル基含有感光性樹脂を提供することを目的とするものである。
さらに本発明の目的は、一般のプリント配線板のソルダーレジストや、フレキシブルプリント配線板やテープキャリアパッケージの製造に用いられるソルダーレジストや、ビルドアップ基板等の多層配線板の層間絶縁層などに要求される密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性等の特性を維持もしくは向上させ、かつ、特にＩＣパッケージに要求される耐吸湿性並びにＰＣＴ（プレッシャークッカー）耐性等の特性に優れる硬化膜が得られ、プリント配線板の高密度化、面実装化に対応可能でアルカリ現像可能な液状の光硬化性・熱硬化性組成物及びそれから得られる硬化膜を提供することにある。
発明の開示
前記目的を達成するために、本発明の一側面によれば、ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られ、３０〜１５０ｍｇＫＯＨ／ｇの範囲内にある酸価を有するカルボキシル基含有感光性樹脂（Ａ）が提供される。
本発明のより具体的な好適な態様によれば、多塩基酸無水物（ｆ）が脂環式二塩基酸無水物であるカルボキシル基含有感光性樹脂（Ａ）が提供される。
本発明のカルボキシル基含有感光性樹脂は、ノボラック型フェノール樹脂のアルキレンオキシドの付加反応による鎖延長によって可撓性、伸びの向上がなされ、アルキレンオキシドの付加反応によって生じた末端水酸基にアクリル酸及び／又はメタクリル酸の付加及び多塩基酸無水物の付加を行なうことによって、不飽和基やカルボキシル基が側鎖の末端に付与されたものであるため、反応性が向上し、鎖延長と併せ持って高いレベルで耐熱性と強靱性のバランスがとれ、硬度、可撓性に優れると共に、耐水性、耐薬品性等にも優れた硬化物が得られる。また、末端カルボキシル基を有するためアルカリ水溶液による現像も可能である。
本発明の他の側面によれば、（Ａ）ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られるカルボキシル基含有感光性樹脂、（Ｃ）光重合開始剤、及び（Ｄ）エポキシ樹脂を含有することを特徴とするアルカリ現像可能な光硬化性・熱硬化性組成物、あるいは上記各成分に加えてさらに（Ｂ）感光性（メタ）アクリレート化合物を含有することを特徴とするアルカリ現像可能な光硬化性・熱硬化性組成物が提供される。
好適な態様によれば、上記各成分に加えてさらに（Ｅ）有機溶剤及び／又は（Ｆ）硬化触媒を含有することを特徴とするアルカリ現像可能な光硬化性・熱硬化性組成物が提供される。
さらに本発明の他の側面によれば、前記アルカリ現像可能な光硬化性・熱硬化性組成物から得られる硬化物もまた提供される。その好適な一態様においては、該組成物を、基材、例えば回路形成されたプリント配線板表面に、スクリーン印刷法、ロールコーティング法、カーテンコーティング法、スプレーコーティング法などの方法により塗布し、遠赤外線乾燥炉や熱風乾燥炉等で乾燥し、続いてレーザー光等の活性エネルギー線をパターン通りに直接照射するか、又はパターン形成したフォトマスクを通して高圧水銀灯、超高圧水銀灯、メタルハライドランプ、無電極ランプなどを用いて活性エネルギー線を照射し、その後未露光部をアルカリ水溶液で現像して所定のパターンを形成する。その後、加熱処理、又は活性エネルギー線照射後の加熱処理、もしくは加熱処理後の活性エネルギー照射により仕上げ硬化(本硬化)させることにより、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性等の諸特性に優れた硬化膜（硬化物）を低コストで生産性良く形成できる。
発明を実施するための最良の形態
本発明者らは、前記の課題を解決するため鋭意検討を重ねた結果、ノボラック型フェノール樹脂のアルキレンオキシド付加物に不飽和基含有モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、特に不飽和基含有モノカルボン酸がアクリル酸又は／及びメタクリル酸であり、多塩基酸無水物が脂環式二塩基酸無水物であるカルボキシル基含有感光性樹脂（Ａ）は、現像性、光硬化性及び熱硬化性に優れると共に、優れた耐熱性と強靱性を併せ持つ硬化物を与え、該カルボキシル基含有感光性樹脂（Ａ）を光重合開始剤（Ｃ）及びエポキシ樹脂（Ｄ）と共に含有し、あるいはこれらに加えてさらに感光性（メタ）アクリレート化合物（Ｂ）を含有する光硬化性・熱硬化性組成物から得られる硬化物は、レジストとして必要な前記のような優れた特性を持つことを見出し、本発明を完成させるに至ったものである。
すなわち、本発明のカルボキシル基含有感光性樹脂（Ａ）は、ノボラック型フェノール樹脂のアルキレンオキシドの付加反応による鎖延長によって可撓性、伸びに優れた主鎖を形成し、かつ、アルキレンオキシドの付加反応によって生じた末端水酸基にアクリル酸及び／又はメタクリル酸の付加及び多塩基酸無水物の付加が行なわれ、不飽和基やカルボキシル基が同一側鎖上に存在せず、かつそれぞれ側鎖の末端に位置するため、反応性に優れ、高い耐熱性と強靱性を有し、また、主鎖から離れた末端カルボキシル基の存在により優れたアルカリ現像性を有し、しかも該樹脂は、従来技術で用いられているエポキシアクリレートの酸無水物変成樹脂のように反応性の低い親水性の２級水酸基を有しないため、耐水性、耐薬品性に富む硬化物を与える。
従って、該カルボキシル基含有感光性樹脂（Ａ）を光重合開始剤（Ｃ）及びエポキシ樹脂（Ｄ）と共に含有し、あるいはこれらに加えてさらに感光性（メタ）アクリレート化合物（Ｂ）を含有する液状の光硬化性・熱硬化性組成物は、優れたアルカリ現像性、光硬化性及び熱硬化性を示すと共に、その塗膜の選択的露光、現像及び仕上げ硬化によって、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性に優れた硬化物が得られるものである。
以下、本発明のカルボキシル基含有感光性樹脂及びそれを含有する光硬化性・熱硬化性組成物の各成分について詳細に説明する。
まず、本発明のカルボキシル基含有感光性樹脂（Ａ）は、前記したように、ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸 及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られる。各反応は、後述するような触媒を用い、溶媒中又は無溶媒下で容易に行なわれる。
このようなカルボキシル基含有感光性樹脂（Ａ）は、３０〜１５０ｍｇＫＯＨ／ｇ、好ましくは５０〜１２０ｍｇＫＯＨ／ｇの範囲内にある酸価を有することが望ましい。カルボキシル基含有感光性樹脂の酸価が３０ｍｇＫＯＨ／ｇよりも低いときは、アルカリ水溶液に対する溶解性が悪くなり、形成した塗膜の現像が困難になる。一方、１５０ｍｇＫＯＨ／ｇよりも高くなると、露光の条件によらず露光部の表面まで現像されてしまい、好ましくない。
上記ノボラック型フェノール樹脂（ａ）は、フェノール類とホルムアルデヒドとの縮合反応によって得られるが、通常、これらの反応は酸性触媒の存在下で行なわれる。
フェノール類としては、フェノール、クレゾール、エチルフェノール、プロピルフェノール、ブチルフェノール、ヘキシルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、クミルフェノール等が挙げられる。
上記ノボラック型フェノール樹脂（ａ）に対するアルキレンオキシド（ｂ）の付加割合は、ノボラック型フェノール樹脂（ａ）のフェノール性水酸基１当量当り、０．３〜１０．０モルが好ましい。０．３モル未満の場合、カルボキシ基含有感光性樹脂において、光硬化性が乏しくなる恐れがある。また、１０．０モルより多い場合、熱硬化性が乏しくなる恐れがある。
ノボラック型フェノール樹脂（ａ）に対するアルキレンオキシド（ｂ）の付加反応は、例えば、水酸化ナトリウムのようなアルカリ金属化合物、又は、トリメチルベンジルアンモニウムハイドロオキサイド、テトラメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムハイドロオキサイド等の第四級塩基性塩化合物、又は、アルカリ金属化合物と第四級塩基性塩化合物の混合物の存在下において、例えば、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類、メチルエチルケトン、シクロヘキサノン、メチルイソブチルケトン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、及びこれらの混合溶媒を用いて、８０〜１８０℃、常圧〜１０ｋｇ／ｃｍ２で行なわれる。特にケトン類及び芳香族炭化水素類を単独で又は２種以上を混合した溶媒が好適に用いられる。
アルキレンオキシド（ｂ）としては、エチレンオキシド、プロピレンオキシド、トリメチレンオキシド、テトラヒドロフラン、テトラヒドロピラン等が挙げられる。
上記ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）の反応生成物（ｃ）と、アクリル酸及び／又はメタクリル酸（ｄ）とのエステル化反応における反応温度は、約５０〜１５０℃が好ましく、減圧下、常圧下、加圧下のいずれでも反応を行なうことができる。反応溶媒としては、ｎ−ヘキサン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン、トリクロロエタン、テトラクロロエチレン、メチルクロロホルム、ジイソプロピルエーテル、及び、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類等が好適に用いられる。これらの溶媒は単独で又は２種以上を混合して用いることができる。エステル化触媒としては、硫酸、塩酸、燐酸、フッ化ホウ素、メタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、カチオン交換樹脂等が適宜用いられる。エステル化反応は重合禁止剤の存在下で行なうのが好ましく、重合禁止剤としては、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等が好適に用いられる。
前記不飽和基含有モノカルボン酸としては、光反応性と硬化物物性、特に耐熱性、耐吸湿性及び電気特性に与える影響から、アクリル酸及び／又はメタクリル酸が好ましく、単独で又は２種以上を混合して用いることができる。
前記反応生成物（ｃ）とアクリル酸及び／又はメタクリル酸（ｄ）の反応生成物（ｅ）に、多塩基酸無水物（ｆ）を反応させて本発明のカルボキシル基含有感光性樹脂（感光性プレポリマー）が得られるが、この反応において、多塩基酸無水物（ｆ）の使用量は、生成するカルボキシル基含有感光性樹脂（Ａ）の酸価が、好ましくは３０〜１５０ｍｇＫＯＨ／ｇ、より好ましくは５０〜１２０ｍｇＫＯＨ／ｇとなるような付加量とする。反応は、後述する有機溶剤の存在下又は非存在下でハイドロキノンや酸素等の重合禁止剤の存在下、通常、約５０〜１５０℃で行なう。このとき必要に応じて、トリエチルアミン等の三級アミン、トリエチルベンジルアンモニウムクロライド等の４級アンモニウム塩、２−エチル−４−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン等のリン化合物等を触媒として添加してもよい。
上記多塩基酸無水物（ｆ）としては、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、３，６−エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸等の脂環式二塩基酸無水物；無水コハク酸、無水マレイン酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、無水トリメリット酸等の脂肪族又は芳香族二塩基酸無水物、あるいはビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられ、これらのうち１種又は２種以上を使用することができる。これらの中でも、脂環式二塩基酸無水物が特に好ましい。
また、他のカルボキシル基含有感光性樹脂、例えば、ノボラック型及び／又はビスフェノール型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂等を、特性向上の目的で本発明のカルボキシル基含有感光性樹脂と混合することができる。
前記感光性（メタ）アクリレート化合物（Ｂ）としては、１分子中に１個以上の（メタ）アクリロイル基を有する室温で液体、固体又は半固形の感光性（メタ）アクリレート化合物が使用できる。これら感光性（メタ）アクリレート化合物の使用目的は、組成物の光反応性を上げることにある。室温で液状の感光性（メタ）アクリレート化合物は、組成物の光反応性を上げる目的の他、組成物を各種の塗布方法に適した粘度に調整したり、アルカリ水溶液への溶解性を助ける役割も果たす。しかし、室温で液状の感光性（メタ）アクリレート化合物を多量に使用すると、塗膜の指触乾燥性が得られず、また塗膜の特性も悪化する傾向があるので、多量に使用することは好ましくない。感光性（メタ）アクリレート化合物（Ｂ）の配合量は、前記カルボキシル基含有感光性樹脂（Ａ）１００質量部（固形分として、以下同様）に対して５０質量部以下が好ましい。
前記感光性（メタ）アクリレート化合物（Ｂ）としては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレートなどの水酸基含有のアクリレート類；ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレートなどの水溶性のアクリレート類；トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレートなどの多価アルコールの多官能ポリエステルアクリレート類；トリメチロールプロパン、水添ビスフェノールＡ等の多官能アルコールもしくはビスフェノールＡ、ビフェノールなどの多価フェノールのエチレンオキサイド付加物及び／又はプロピレンオキサイド付加物のアクリレート類；上記水酸基含有アクリレートのイソシアネート変成物である多官能もしくは単官能ポリウレタンアクリレート；ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル又はフェノールノボラックエポキシ樹脂の（メタ）アクリル酸付加物であるエポキシアクリレート類、及び上記アクリレート類に対応するメタクリレート類などが挙げられ、これらは単独で又は２種以上を使用することができる。これらの中でも、１分子中に２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレート化合物が好ましい。
前記光重合開始剤（Ｃ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１- オン、Ｎ，Ｎ- ジメチルアミノアセトフェノン等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾイルパーオキシド、クメンパーオキシド等の有機過酸化物；２，４，５−トリアリールイミダゾール二量体、リボフラビンテトラブチレート、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾチアゾール等のチオール化合物；２，４，６−トリス−ｓ−トリアジン、２，２，２−トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物；ベンゾフェノン、４，４´−ビスジエチルアミノベンゾフェノン等のベンゾフェノン類又はキサントン類；２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイドなどが挙げられる。これら公知慣用の光重合開始剤は、単独で又は２種類以上の混合物として使用でき、さらにはＮ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類などの光開始助剤を加えることができる。また可視光領域に吸収のあるＣＧＩ−７８４等（チバ・スペシャルティ・ケミカルズ（株）製）のチタノセン化合物等も、光反応を促進するために添加することもできる。特に好ましい光重合開始剤は、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン等であるが、特にこれらに限られるものではなく、紫外光もしくは可視光領域で光を吸収し、（メタ）アクリロイル基等の不飽和基をラジカル重合させるものであれば、光重合開始剤、光開始助剤に限らず、単独であるいは複数併用して使用できる。そして、その使用量は前記カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して０. ５〜２５質量部の割合が好ましい。
前記エポキシ樹脂（Ｄ）としては、具体的には、ジャパンエポキシレジン（株）製のエピコート８２８、エピコート８３４、エピコート１００１、エピコート１００４、大日本インキ化学工業（株）製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成（株）製のエポトートＹＤ−０１１、ＹＤ−０１３、ＹＤ−１２７、ＹＤ−１２８、ダウケミカル（株）製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、住友化学工業（株）製のスミ−エポキシＥＳＡ−０１１、ＥＳＡ−０１４、ＥＬＡ−１１５、ＥＬＡ−１２８（何れも商品名）等のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ９０３、大日本インキ化学工業（株）製のエピクロン１５２、エピクロン１６５、東都化成（株）製のエポトートＹＤＢ−４００、ＹＤＢ−５００、ダウケミカル（株）製のＤ．Ｅ．Ｒ．５４２、住友化学工業（株）製のスミ−エポキシＥＳＢ−４００、ＥＳＢ−７００（何れも商品名）等のブロム化エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５２、エピコート１５４、ダウケミカル（株）製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、大日本インキ化学工業（株）製のエピクロンＮ−７３０、エピクロンＮ−７７０、エピクロンＮ−８６５、東都化成（株）製のエポトートＹＤＣＮ−７０１、ＹＤＣＮ−７０４、日本化薬（株）製のＥＰＰＮ−２０１、ＥＯＣＮ−１０２５、ＥＯＣＮ−１０２０，ＥＯＣＮ−１０４Ｓ、ＲＥ−３０６、住友化学工業（株）製のスミ−エポキシＥＳＣＮ−１９５Ｘ、ＥＳＣＮ−２２０（何れも商品名）等のノボラック型エポキシ樹脂；大日本インキ化学工業（株）製のエピクロン８３０、ジャパンエポキシレジン製エピコート８０７、東都化成（株）製のエポトートＹＤＦ−１７０、ＹＤＦ−１７５、ＹＤＦ−２００４（何れも商品名）等のビスフェノールＦ型エポキシ樹脂；東都化成（株）製のエポトートＳＴ−２００４、ＳＴ−２００７、ＳＴ−３０００（何れも商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート６０４、東都化成（株）製のエポトートＹＨ−４３４、住友化学工業（株）製のスミ−エポキシＥＬＭ−１２０（何れも商品名）等のグリシジルアミン型エポキシ樹脂；ダイセル化学工業（株）製のセロキサイド２０２１（商品名）等の脂環式エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−９３３、日本化薬（株）製のＥＰＰＮ−５０１、ＥＰＰＮ−５０２（何れも商品名）等のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−６０５６、ＹＸ−４０００、ＹＬ−６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬（株）製のＥＢＰＳ−２００、旭電化工業（株）製のＥＰＸ−３０、大日本インキ化学工業（株）製のＥＸＡ−１５１４（何れも商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ−９３１（商品名）等のテトラフェニロールエタン型エポキシ樹脂；日産化学（株）製のＴＥＰＩＣ（商品名）等の複素環式エポキシ樹脂；日本油脂（株）製のブレンマーＤＧＴ（商品名）等のジグリシジルフタレート樹脂；東都化成（株）製のＺＸ−１０６３（商品名）等のテトラグリシジルキシレノイルエタン樹脂；新日鉄化学（株）製のＥＳＮ−１９０、ＥＳＮ−３６０、大日本インキ化学工業（株）製のＨＰ−４０３２、ＥＸＡ−４７５０、ＥＸＡ−４７００（何れも商品名）等のナフタレン基含有エポキシ樹脂；大日本インキ化学工業（株）製のＨＰ−７２００、ＨＰ−７２００Ｈ（何れも商品名）等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂（株）製のＣＰ−５０Ｓ、ＣＰ−５０Ｍ（何れも商品名）等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにヒダントイン型エポキシ樹脂、シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂等が挙げられるが、これらに限られるものではない。これらエポキシ樹脂は単独で又は２種以上を用いることができる。これらの中でも特にビフェノール型もしくはビキシレノール型エポキシ樹脂又はそれらの混合物が好ましい。
前記のようなエポキシ樹脂（Ｄ）は、熱硬化することにより、レジストの密着性、耐熱性等の特性を向上させる。その配合量は、前記カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して１０質量部以上、７０質量部以下の割合で充分であり、好ましくは１５〜６０質量部の割合である。エポキシ樹脂（Ｄ）の配合量が上記範囲未満の場合、硬化膜の吸湿性が高くなってＰＣＴ耐性が低下し易くなり、またはんだ耐熱性や耐無電解めっき性も低くなり易い。一方、上記範囲を超えると、塗膜の現像性や硬化膜の耐無電解めっき性が悪くなり、またＰＣＴ耐性も劣ったものとなる。
また、本発明の光硬化性・熱硬化性組成物は、前記カルボキシル基含有感光性樹脂（Ａ）や感光性（メタ）アクリレート化合物（Ｂ）を溶解させ、また組成物を塗布方法に適した粘度に調整するために、有機溶剤（Ｅ）を配合することができる。有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられる。これらの有機溶剤は、単独で又は２種類以上の混合物として使用することができる。なお、有機溶剤の配合量は、塗布方法に応じた任意の量とすることができる。
さらに本発明の光硬化性・熱硬化性組成物は、その熱硬化特性を向上させるために硬化触媒（Ｆ）を含有することが好ましい。硬化触媒（Ｆ）としては、例えば、イミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、４−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール等のイミダゾール誘導体；ジシアンジアミド、ベンジルジメチルアミン、４−（ジメチルアミノ）−Ｎ，Ｎ−ジメチルベンジルアミン、４−メトキシ−Ｎ，Ｎ−ジメチルベンジルアミン、４−メチル−Ｎ，Ｎ−ジメチルベンジルアミン等のアミン化合物、アジピン酸ヒドラジド、セバシン酸ヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物などを用いることができる。市販されているものとしては、例えば四国化成（株）製の２ＭＺ−Ａ、２ＭＺ−ＯＫ、２ＰＨＺ、２Ｐ４ＢＨＺ、２Ｐ４ＭＨＺ（いずれもイミダゾール系化合物の商品名）、サンアプロ（株）製のＵ−ＣＡＴ３５０３Ｘ、Ｕ−ＣＡＴ３５０２Ｘ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ−ＣＡＴＳＡ１０２、Ｕ−ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂の硬化触媒、もしくはエポキシ基とカルボキシル基の反応を促進するものであればよく、単独で又は２種以上を混合して使用してもかまわない。また、密着性付与剤としても機能するグアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、２，４−ジアミノ−６−メタクリロイルオキシエチル−Ｓ−トリアジン、２−ビニル−２，４−ジアミノ−Ｓ−トリアジン、２−ビニル−４，６−ジアミノ−Ｓ−トリアジン・イソシアヌル酸付加物、２，４−ジアミノ−６−メタクリロイルオキシエチル−Ｓ−トリアジン・イソシアヌル酸付加物等のＳ−トリアジン誘導体を用いることもでき、好ましくはこれらの化合物を前記硬化触媒と併用する。上記硬化触媒の配合量は通常の量的割合で充分であり、例えば前記カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して０．１〜２０質量部、好ましくは０．５〜１５．０質量部の割合である。
本発明の光硬化性・熱硬化性組成物には、さらに必要に応じて、硫酸バリウム、チタン酸バリウム、酸化ケイ素粉、微粉状酸化ケイ素、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、マイカ等の公知慣用の無機フィラーを単独で又は２種以上配合することができる。これらは塗膜の硬化収縮を抑制し、密着性、硬度などの特性を向上させる目的で用いられる。無機フィラーの配合量は、前記カルボキシル基含有感光性樹脂（Ａ）１００質量部当り１０〜３００質量部、好ましくは３０〜２００質量部の割合が適当である。
本発明の組成物は、さらに必要に応じてフタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ−ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤などのような公知慣用の添加剤類を配合することができる。
以上のような組成を有する本発明の光硬化性・熱硬化性組成物は、必要に応じて希釈して塗布方法に適した粘度に調整し、これを例えば、回路形成されたプリント配線板にスクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば約６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。その後、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、又はパターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成でき、さらに、加熱硬化のみ、又は活性エネルギー線の照射後加熱硬化もしくは加熱硬化後活性エネルギー線の照射で最終硬化（本硬化）させることにより、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性に優れた硬化膜（硬化物）が形成される。
上記アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。
また、光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどが適当である。その他、レーザー光線なども活性エネルギー線として利用できる。
以下、本発明の実施例等により具体的に説明するが本発明はこれら実施例に限定されるものではない。なお、以下において特に断りのない限り、「部」は質量部を意味するものとする。
カルボキシル基含有感光性樹脂の調製
合成例１
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、群栄化学工業（株）製ノボラック型クレゾール樹脂（商品名「レジトップＰＳＦ―２８０３」、ＯＨ当量：１０９）１０９部、５０％水酸化ナトリウム水溶液２．６部、トルエン／メチルイソブチルケトン（質量比＝２／１）１００部を仕込み、撹拌しつつ系内を窒素置換し、次に加熱昇温し、１５０℃、８ｋｇ／ｃｍ２でプロピレンオキシド６０部を徐々に導入し反応させた。反応はゲージ圧０．０ｋｇ／ｃｍ２となるまで約４時間を続けた後、室温まで冷却した。この反応溶液に３．３部の３６％塩酸水溶液を添加混合し、水酸化ナトリウムを中和した。この中和反応生成物をトルエンで希釈し、３回水洗し、エバポレーターにて脱溶剤して、水酸基価が１６７ｇ／ｅｑ．であるノボラック型クレゾール樹脂のアルキレンオキシド付加物を得た。これは、フェノール性水酸基１当量当りアルキレンオキシドが平均１モル付加しているものであった。
得られたノボラック型クレゾール樹脂のアルキレンオキシド付加物１２２部、アクリル酸３４部、ｐ−トルエンスルホン酸３．０部、ハイドロキノンモノメチルエーテル０．０５部、トルエン１００部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を吹き込みながら攪拌して、１１０℃で６時間反応させた。反応により生成した水がトルエンとの共沸混合物として留出し始めた後、さらに５時間反応させ、室温まで冷却した。得られた反応溶液を５％ＮａＣｌ水溶液を用いて水洗し、エバポレーターにてトルエンを留去し、ジエチレングリコールモノエチルエーテルアセテートを加えて、不揮発分６０％のノボラック型アクリレート樹脂溶液を得た。
次に、撹拌器及び還流冷却器の付いた４つ口フラスコに、得られたノボラック型アクリレート樹脂溶液１７０部、ハイドロキノンモノメチルエーテル０．０５部、ピリジン０．２部を仕込み、この混合物を１２０℃に加熱し、テトラヒドロ無水フタル酸２３部を加え、６時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６４％、固形分酸価６７ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＡ−１ワニスと称す。得られたカルボキシル基含有感光性樹脂の赤外吸収スペクトル（ＩＲスペクトル）を図１に示す。
合成例２
合成例１と同様にして得られた水酸基価が１６７ｇ／ｅｑ．のノボラック型クレゾール樹脂のアルキレンオキシド付加物１２２部、アクリル酸２６部、ｐ−トルエンスルホン酸２．０部、ハイドロキノンモノメチルエーテル０．０５部、トルエン１００部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を吹き込みながら撹拌して、１１０℃で６時間反応させた。反応により生成した水がトルエンとの共沸混合物として留出し始めた後、さらに５時間反応させ、室温まで冷却した。得られた反応溶液を５％ＮａＣｌ水溶液を用いて水洗し、エバポレーターにてトルエンを留去し、ジエチレングリコールモノエチルエーテルアセテートを加えて、不揮発分６１％のノボラック型アクリレート樹脂溶液を得た。
次に、撹拌器及び還流冷却器の付いた４つ口フラスコに、得られたノボラック型アクリレート樹脂溶液１７９部、ハイドロキノンモノメチルエーテル０．０５部、ピリジン０．３５部を仕込み、この混合物を１２０℃に加熱し、テトラヒドロ無水フタル酸４１．３部を加え、６時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６８％、固形分酸価１００ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＡ−２ワニスと称す。
合成例３
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、昭和高分子株式会社製ノボラック型クレゾール樹脂（商品名「ショーノールＣＲＧ９５１」、ＯＨ当量：１１９．４）１１９．４部、水酸化カリウム１．１９部、トルエン１１９．４部を仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド６３．８部を徐々に滴下し、１２５〜１３２℃、０〜４．８ｋｇ／ｃｍ２で１６時間反応させた。その後、室温まで冷却し、この反応溶液に８９％リン酸１．５６部を添加混合し、水酸化カリウムを中和し、不揮発分６２．１％、水酸基価が１８２．２ｇ／ｅｑ．であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基１当量当りアルキレンオキシドが平均約１．０８モル付加しているものであった。
得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液２９３．０部、アクリル酸４３．２部、メタンスルホン酸１１．５３部、メチルハイドロキノン０．１８部、トルエン２５２．９部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１１０℃で１２時間反応させた。反応により生成した水はトルエンとの共沸混合物として、１２．６部の水が留出した。その後、室温まで冷却し、得られた反応溶液を１５％水酸化ナトリウム水溶液３５．３５部で中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１部で置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。
次に、得られたノボラック型アクリレート樹脂溶液３３２．５部、トリフェニルホスフィン１．２２部を撹拌器、温度計、空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６０．８部を徐々に加え、９５〜１０１℃で６時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分７０．６％、固形分酸価８７．７ｍｇＫＯＨ／ｇであった。以下、この樹脂溶液をＡ−３ワニスと称す。得られたカルボキシル基含有感光性樹脂の１Ｈ−ＮＭＲスペクトルを図２に、ＩＲスペクトルを図３に示す。
合成例４
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、群栄化学工業（株）製ノボラック型クレゾール樹脂（商品名「レジトップＰＳＦ−２８０３」、ＯＨ当量：１０９）１０９部、水酸化カリウム１．０９部、トルエン１０９部を仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド３４８部を徐々に滴下し、１２５〜１３２℃、０〜４．８ｋｇ／ｃｍ２で１６時間反応させた。その後、室温まで冷却し、この反応溶液に８９％リン酸１．２部を添加混合し、水酸化カリウムを中和し、不揮発分８４．３％、水酸基価が４４４．８ｇ／ｅｑ．であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基１当量当りアルキレンオキシドが平均５．７９モル付加しているものであった。
得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液５４２．１部、アクリル酸３６部、メタンスルホン酸９部、メチルハイドロキノン０．２部、トルエン３８２部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１１０℃で１２時間反応させた。反応により生成した水はトルエンとの共沸混合物として、７．６部の水が留出した。その後、室温まで冷却し、得られた反応溶液を１５％水酸化ナトリウム水溶液２６部で中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート３４０部で置換しつつ留去し、不揮発分５８％のノボラック型アクリレート樹脂溶液を得た。
次に、得られたノボラック型アクリレート樹脂溶液４１８．５部、トリフェニルホスフィン０．７６部を撹拌器、温度計、空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物３８部を徐々に加え、１０７〜１１９℃で３時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６３．８％、固形分酸価５９．９ｍｇＫＯＨ／ｇであった。以下、この樹脂溶液をＡ−４ワニスと称す。得られたカルボキシル基含有感光性樹脂の１Ｈ−ＮＭＲスペクトルを図４に、ＩＲスペクトルを図５に示す。
合成例５
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、群栄化学工業（株）製ノボラック型クレゾール樹脂（商品名「レジトップＰＳＦ―２８０３」、ＯＨ当量：１０９）１５０部、５０％水酸化ナトリウム水溶液３．０部、エチレングリコールモノエチルエーテルアセテート１５０部を仕込み、撹拌しつつ系内を窒素置換し、次に加熱昇温し、１５０℃、８ｋｇ／ｃｍ２でプロピレンオキシド５６部を徐々に導入し反応させた。反応はゲージ圧０．０ｋｇ／ｃｍ２となるまで約４時間続けた後、室温まで冷却した。この反応溶液に３．８部の３６％塩酸水溶液を添加混合し、水酸化ナトリウムを中和した。この中和反応生成物をトルエンで希釈し、３回水洗し、エバポレーターにて脱溶剤して、ジエチレングリコールモノエチルエーテルアセテートを加えて、不揮発分８０％、固形分換算の水酸基価が１４９ｇ／ｅｑであるノボラック型クレゾール樹脂のアルキレンオキシド付加物を得た。これは、フェノール性水酸基１当量当りアルキレンオキシドが平均０．７モル付加したものであった。
得られたノボラック型クレゾール樹脂のアルキレンオキシド付加物１８７部、アクリル酸２５部、ｐ−トルエンスルホン酸２．０部、ハイドロキノンモノメチルエーテル０．０２部、トルエン７０部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を５０ｍｌ／分の速度で吹き込み、撹拌しながら、１１０℃で５時間反応させた。反応により生成した水がトルエンとの共沸混合物として留出し始めた後、さらに５時間反応させた。得られた反応溶液を５％ＮａＣｌ水溶液を用いて水洗し、エバポレーターにてトルエンを留去し、ジエチレングリコールモノエチルエーテルアセテートを加えて、不揮発分５５％のノボラック型アクリレート樹脂溶液を得た。
次に、撹拌器及び還流冷却器の付いた４つ口フラスコに、得られたノボラック型アクリレート樹脂溶液２３８部、ハイドロキノンモノメチルエーテル０．０２部、トリフェニルホスフィン１．３部を仕込み、この混合物を１２０℃に加熱し、テトラヒドロフタル酸無水物３９部を加え、６時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６１％、固形分酸価８３ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＡ−５ワニスと称す。
比較合成例１
クレゾールノボラック型エポキシ樹脂のエピクロンＮ−６９５（大日本インキ化学工業（株）製、エポキシ当量：２２０）２２０部を撹拌機及び還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート２２０部を加え、加熱溶解した。次に、重合禁止剤としてハイドロキノン０．４６部と、反応触媒としてトリフェニルフホスフィン１．３８部を加えた。この混合物を９５〜１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、１６時間反応させた。この反応生成物を、８０〜９０℃まで冷却し、テトラヒドロフタル酸無水物１０６部を加え、８時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６４％、固形物の酸価９７ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＢ−１ワニスと称す。
比較合成例２
クレゾールノボラック型エポキシ樹脂のＥＣＯＮ−１０４Ｓ（日本化薬（株）製、エポキシ当量：２２０）２２０部を撹拌機及び還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート２２０部を加え、加熱溶解した。次に、重合禁止剤としてメチルハイドロキノン０．４６部と、反応触媒としてトリフェニルホスフィン１．３８部を加えた。この混合物を９５〜１０５℃に加熱し、アクリル酸５０．４部、ｐ−ヒドロキシフェネチルアルコール４１．５部を徐々に滴下し、１６時間反応させた。この反応生成物を、８０〜９０℃まで冷却し、テトラヒドロフタル酸無水物１１６部を加え、８時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６６％、固形物の酸価９８ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＢ−２ワニスと称す。
比較合成例３
ガス導入管、撹拌装置、冷却管及び温度計を備えたフラスコにビスフェノールＡ３１３部とビスフェノールＡ型エポキシ樹脂（エピクロン−８４０、大日本インキ化学工業（株）製、エポキシ当量：１８０）９８７部を仕込み、窒素雰囲気下にて、撹拌下１２０℃で溶解させた。その後、トリフェニルホスフィン０．６５部を添加し、フラスコ内の温度を１５０℃まで昇温し、温度を１５０℃で保持しながら、約９０分間反応させ、エポキシ当量４７５ｇ／ｅｑ．のエポキシ化合物を得た。次にフラスコ内の温度を７０℃以下まで冷却し、エピクロルヒドリン１８５１部、ジメチルスルホキシド１６９０部を加え、撹拌下７０℃まで昇温し保持した。その後、９６％水酸化ナトリウム１１０部を９０分間かけて分割添加した後、さらに３時間反応させた。反応終了後、過剰のエピクロルヒドリン及びジメチルスルホキシドの大半を１２０℃、５０ｍｍＨｇの減圧下にて蒸留し、副生塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケトンに溶解させ、水洗した。その後、油層よりメチルイソブチルケトンを蒸留回収して、エポキシ当量３３６ｇ／ｅｑ．の多核エポキシ化合物を得た。次に、上記多核エポキシ化合物３３６部を撹拌装置、冷却管及び温度計を備えたフラスコに入れ、カルビトールアセテート３００部を加え、加熱溶解し、メチルハイドロキノン０．４６部と、トリフェニルホスフィン１．３８部を加え、９５〜１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、１６時間反応させた。この反応生成物を、８０〜９０℃まで冷却し、テトラヒドロフタル酸無水物１５２部を加え、８時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有感光性樹脂は、不揮発分６５％、固形物の酸価９８ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＢ−３ワニスと称す。
光硬化性・熱硬化性樹脂組成物の調製
組成例１〜５及び比較組成例１〜３
前記合成例１〜５及び比較合成例１〜３で得られた各ワニスを用いた表１に示す配合成分を、３本ロールミルで混練し、光硬化性・熱硬化性樹脂組成物を得た。各組成の特性値を表２に示す。
【表１】

Figure 0003964326
【表２】
Figure 0003964326
上記表２中の性能試験の評価方法は以下の通りである。
（１）ガラス転移点
予め水洗・乾燥を行なったテフロン板に、上記各組成例及び比較組成例の組成物をスクリーン印刷法で塗布し、熱風循環式乾燥炉で８０℃で４０分乾燥させた。これを室温まで冷却した後、露光量１０００ｍＪ／ｃｍ２の条件で露光し、熱風循環式乾燥炉で硬化を１５０℃で６０分間行なった。これを室温まで冷却した後、テフロン板から硬化塗膜をはがし、評価サンプルを得た。この評価サンプルのガラス転移点をＤＭＡ法により測定した。
（２）引張弾性率、（３）引張強度（引張破壊強さ）、（４）伸び率（引張破壊伸び）
上記の評価サンプルの引張弾性率、引張強度（引張破壊強さ）、伸び率（引張破壊伸び）を引張−圧縮試験機（（株）島津製作所製）によって測定した。
予め水洗・乾燥を行なったカプトン材（厚さ２５μｍ）に、上記各組成例及び比較組成例の組成物をスクリーン印刷法で塗布し、熱風循環式乾燥炉で８０℃で４０分乾燥させた。これを室温まで冷却した後、露光量１０００ｍＪ／ｃｍ２の条件で露光し、熱風循環式乾燥炉で硬化を１５０℃で６０分間行ない、耐折性試験及び柔軟性試験用の評価サンプルを得た。
（５）耐折性
硬化膜を外側にして１８０゜折り曲げ、以下の基準で評価した。
○：硬化膜にクラックがないもの
△：硬化膜に若干クラックがあるもの
×：硬化膜にクラックがあるもの
（６）柔軟性
硬化膜を幅１０ｍｍ、長さ９０ｍｍに加工して作製したフィルム状試験片の一側辺部を電子秤上に載せ、他側辺部を折り曲げる方法で、フィルム間が３ｍｍになるまでに電子秤にかかる最大荷重を反発力として、以下の基準で評価した。
○：１０ｇ未満
△：１０〜３０ｇ未満
×：３０ｇ以上
（７）吸水率
予め重量を測定したガラス板に、上記各組成例及び比較組成例の組成物をスクリーン印刷法で塗布し、熱風循環式乾燥炉で８０℃で４０分乾燥させた。これを室温まで冷却した後、露光量１０００ｍＪ／ｃｍ２の条件で露光し、熱風循環式乾燥炉で硬化を１５０℃で６０分間行ない、評価サンプルを得た。これを室温まで冷却した後、評価サンプルの重量を測定した。次に、この評価サンプルをＰＣＴ装置（ＴＡＢＡＩ ＥＳＰＥＣ ＨＡＳＴ ＳＹＳＴＥＭ ＴＰＣ−４１２ＭＤ）を用いて１２１℃、１００％Ｒ．Ｈ．の条件で２４時間処理し、処理後の硬化物の重量を測定し、下記算式により硬化物の吸水率を求めた。
吸水率＝｛（Ｗ２−Ｗ１）／（Ｗ１−Ｗｇ）｝×１００
ここで、Ｗ１は評価サンプルの重量、Ｗ２はＰＣＴ処理後の評価サンプルの重量、Ｗｇはガラス板の重量である。
（８）鉛筆硬度：ＪＩＳ Ｋ ５４００に準拠して求めた。
予め水洗・乾燥を行なったプリント配線基板に、上記各組成例及び比較組成例の組成物をスクリーン印刷法で塗布し、熱風循環式乾燥炉で８０℃で４０分乾燥させた。これを室温まで冷却した後、露光量１０００ｍＪ／ｃｍ２の条件で露光し、熱風循環式乾燥炉で硬化を１５０℃で６０分間行ない、耐酸性試験、耐アルカリ性試験及び耐熱性試験用の評価基板を得た。
（９）耐酸性試験
上記評価基板を１０容量％硫酸水溶液に２０℃で３０分間浸漬後取り出し、塗膜の状態と密着性とを総合的に判定評価した。判定基準は以下のとおりである。
○：変化が認められないもの
△：ほんの僅か変化しているもの
×：塗膜にフクレあるいは膨潤脱落があるもの
（１０）耐アルカリ性試験
上記評価基板を、１０容量％硫酸水溶液を１０容量％水酸化ナトリウム水溶液に変えた以外は耐酸性試験と同様に試験評価した。
（１１）耐熱性
上記評価基板を１５０℃の熱風循環乾燥炉に２４時間放置した後、ＪＩＳ Ｋ ５６００−５−６に準拠して１０×１０（１００マス）の碁盤目を作り、テープピーリングによる密着性にて耐熱劣化性を試験評価した。判定基準は以下のとおりである。
○：１００／１００（全く剥がれない）
△：９９／１００〜７０／１００（僅かに剥がれが生じた）
×：６９／１００〜（著しく剥がれた）
表２に示す結果から明らかな如く、本発明のカルボキシル基含有感光性樹脂を用いて得られた組成物の硬化物は、耐熱性、強靱性（引張弾性、引張強度）に優れると共に、伸び、可撓性（耐折性、柔軟性）、吸水率、硬度、耐薬品性にも優れた特性を有している。これに対して、比較例のカルボキシル基含有感光性樹脂を用いて得られた組成物の硬化物は、引張強度、可撓性（耐折性、柔軟性）、伸び、耐湿性（吸水率）が劣っていた。
組成例６〜１０、比較組成例４〜６
表３に示す配合組成に従って各成分を配合し、３本ロールミルでそれぞれ別々に混練し、光硬化性・熱硬化性組成物を調製した。
【表３】
Figure 0003964326
前記組成例６〜１０及び比較組成例４〜６の各光硬化性・熱硬化性組成物をスクリーン印刷法により、１００メッシュのポリエステルスクリーンを用いて２０〜３０μｍの厚さになるように、パターン形成されている銅スルーホールプリント配線基板に全面塗布し、塗膜を８０℃の熱風循環式乾燥炉で所定の時間乾燥し、レジストパターンを有するネガフィルムを塗膜に密着させ、紫外線露光装置（（株）オーク製作所製、型式ＨＭＷ−６８０ＧＷ）を用いて、紫外線を照射した（露光量３５０ｍＪ／ｃｍ２）。次いで１％の炭酸ナトリウム水溶液で６０秒間、２．０ｋｇ／ｃｍ２のスプレー圧で現像し、未露光部分を溶解除去した。その後、１５０℃の熱風循環式乾燥炉で６０分加熱硬化を行ない、得られた硬化膜を有する試験片について、密着性、はんだ耐熱性、ＰＣＴ耐性、無電解金めっき耐性の各試験を行なった。試験方法及び評価方法は次のとおりである。
（１２）現像性：
乾燥時間３０分、４０分、５０分、６０分、７０分、８０分、又は９０分について、露光、現像後の状態を拡大鏡にて目視判定した。結果を表４に示す。
○：現像時、完全に塗膜が除去され、現像できた。
×：現像時、少しでも残渣が残っており、現像されない部分があった。
【表４】
Figure 0003964326
（１３）密着性：
ＪＩＳ Ｄ ０２０２の試験方法に従って硬化膜に碁盤目状にクロスカットを入れ、次いでセロハン粘着テープによるピーリングテスト後の剥れの状態を目視判定した。結果を表５に示す。なお、現像できなかった試験片については評価をしなかった。
◎：１００／１００で全く剥れのないもの
○：１００／１００でクロスカット部が少し剥れたもの
△：５０／１００〜９０／１００
×：０／１００〜５０／１００
【表５】
Figure 0003964326
（１４）はんだ耐熱性：
ＪＩＳ Ｃ ６４８１の試験方法に従って、２６０℃のはんだ浴への試験片の１０秒浸漬を３回行ない、外観の変化を以下の基準で評価した。結果を表６に示す。なお、現像できなかった試験片については評価しなかった。また、ポストフラックス（ロジン系）としては、ＪＩＳ Ｃ ６４８１に従ったフラックスを使用した。
○：外観変化なし
△：硬化膜の変色が認められるもの
×：硬化膜の浮き、剥れ、はんだ潜りあり
【表６】
Figure 0003964326
（１５）吸水率：
予め質量を測定したセラミック基板（アルミナ基板）に前記条件で乾燥時間は４０分として、硬化膜を形成し、総質量を測定する。そして、これを２２℃のイオン交換水に２４時間浸漬した後、質量を測定し、質量の増加率を吸水率とした。結果を表７に示す。
【表７】
Figure 0003964326
（１６）ＰＣＴ耐性：
硬化膜のＰＣＴ耐性を条件１２１℃、飽和５０時間にて以下の基準で評価した。結果を表８に示す。なお、現像できなかった試験片については評価しなかった。
○：硬化膜にふくれ、剥がれ、変色がないもの。
△：硬化膜に若干ふくれ、剥がれ、変色があるもの。
×：硬化膜にふくれ、剥がれ、変色があるもの。
【表８】
Figure 0003964326
（１７）無電解金めっき耐性：
パターン形成されている銅スルーホールプリント配線基板の銅面を表面処理（表面研摩（石井表記（株）製、Ｎｏ．１２００のロール状のバフ研摩後、石井表記（株）製、砥粒Ｎｏ．２７０を使用してジェットスクラブ研摩）し、水洗、乾燥したもの。）し、前記と同様にして、塗布→乾燥→露光→現像→加熱して試験片を得た。この試験片を用いて下記の工程のように無電解金めっきを行ない、その試験片について外観の変化及びセロハン粘着テープを用いたピーリング試験を行ない、硬化膜の剥離状態を判定した。結果を表９に示す。なお、現像できなかった試験片は評価しなかった。
○：外観変化もなく、硬化膜の剥離も全くない。
△：外観の変化はないが、硬化膜にわずかに剥れがある。
×：硬化膜の浮きが見られ、めっき潜りが認められ、ピーリング試験で硬化膜の剥れが大きい。
無電解金めっき工程：
１．脱脂：試験片を３０℃の酸性脱脂液（（株）日本マクダーミッド製、Ｍｅｔｅｘ Ｌ−５Ｂの２０％Ｖｏｌ水溶液）に３分間、浸漬。
２．水洗：流水中に試験片を浸漬、３分間。
３．ソフトエッチ：１４．３％ｗｔ、過硫酸アンモン水溶液に室温で試験片を３分間、浸漬。
４．水洗：流水中に試験片を浸漬、３分間。
５．酸浸漬：１０％Ｖｏｌ．硫酸水溶液に室温で試験片を１分間、浸漬。
６．水洗：流水中に試験片を浸漬、３０秒〜１分間。
７．触媒付与：試験片を３０℃の触媒液（（株）メルテックス製、メタルプレートアクチベーター３５０の１０％Ｖｏｌ．水溶液）に７分間、浸漬。
８．水 洗：流水中に試験片を浸漬、３分間。
９．無電解ニッケルめっき：試験片を８５℃、ｐＨ＝４．６のニッケルめっき液（（株）メルテックス製、メルプレートＮｉ−８６５Ｍ、２０％Ｖｏｌ．水溶液）に２０分間、浸漬。
１０．酸浸漬：１０％Ｖｏｌ．硫酸水溶液に室温で試験片を１分間、浸漬。
１１．水 洗：流水中に試験片を浸漬、３０秒〜１分間。
１２．無電解金めっき：試験片を９５℃、ｐＨ＝６の金めっき液（（株）メルテックス製、オウロレクトロレス ＵＰ １５％Ｖｏｌ．シアン化金カリウム３％Ｖｏｌ．水溶液）に１０分間、浸漬。
１３．水 洗：流水中に試験片を浸漬、３分間。
１４．湯 洗：６０℃の温水に試験片を浸漬、３分間十分に水洗後、水をよくきり、乾燥し、無電解金めっきした試験片を得る。
【表９】
Figure 0003964326
パターン形成されている銅スルーホールプリント配線基板の代わりにカプトン材（厚さ２５μｍ）を用い、前記の方法にて光硬化性・熱硬化性組成物の塗布、硬化を行ない、耐屈曲性、耐折性、柔軟性、反りについて、試験を行なった。
（１８）耐屈曲性：
ＩＰＣ−ＳＭ−８４０Ｂ ＴＭ２．４．２９に従って直径１／８インチ、１０サイクルの条件にて以下の基準で評価した。結果を表１０に示す。なお、現像できなかった試験片については評価しなかった。
○：硬化膜にクラックがないもの
△：硬化膜に若干クラックがあるもの
×：硬化膜にクラックがあるもの
【表１０】
Figure 0003964326
（１９）耐折性：
硬化膜を外側にして１８０゜折り曲げ、以下の基準で評価した。結果を表１１に示す。なお、現像できなかった試験片については評価しなかった。
○：硬化膜にクラックがないもの
△：硬化膜に若干クラックがあるもの
×：硬化膜にクラックがあるもの
【表１１】
Figure 0003964326
（２０）柔軟性：
前記（６）柔軟性の試験と同様の方法、基準で評価した。結果を表１２に示す。なお、現像できなかった試験片については評価しなかった。
【表１２】
Figure 0003964326
（２１）反り：
硬化膜を１５０×１１０ｍｍに加工し、底面からの４角の高さの平均（以下、４角平均値という）を測定算出し、反りを以下の基準で評価した。結果を表１３に示す。なお、現像できなかった試験片については評価しなかった。
○：４角平均値が６ｍｍ未満
△：４角平均値が６ｍｍ以上１２ｍｍ未満
×：４角平均値が１２ｍｍ以上又は丸まって測定不可能
【表１３】
Figure 0003964326
（２２）電気絶縁性：
パターン形成されている銅スルーホールプリント配線基板の代わりに、ＩＰＣで定められたプリント回路基板（厚さ１．６ｍｍ）のＢパターンを用い、前記の方法にて光硬化性・熱硬化性組成物の塗布、硬化を行ない、得られた硬化膜の電気絶縁性を以下の基準にて評価した。
加湿条件：温度８５℃、湿度８５％ＲＨ、印加電圧１００Ｖ、５００時間。
測定条件：測定時間６０秒、印加電圧５００Ｖ。
結果を表１４に示す。なお、現像できなかった試験片については評価しなかった。
○：加湿後の絶縁抵抗値１０９Ω以上、銅のマイグレーションなし。
△：加湿後の絶縁抵抗値１０９Ω以上、銅のマイグレーションあり。
×：加湿後の絶縁抵抗値１０８Ω以下、銅のマイグレーションあり。
【表１４】
Figure 0003964326
産業上の利用可能性
以上のように、本発明のカルボキシル基含有感光性樹脂は、ノボラック型フェノール樹脂のアルキレンオキシドの付加反応による鎖延長によって可撓性、伸びの向上がなされ、アルキレンオキシドの付加反応によって生じた末端水酸基に不飽和基含有モノカルボン酸の付加及び多塩基酸無水物の付加を行なうことによって、不飽和基やカルボキシル基が側鎖の末端に付与されたものであるため、反応性が向上し、鎖延長と併せ持って高いレベルで耐熱性と強靱性のバランスがとれ、硬度、可撓性に優れると共に、耐水性、耐薬品性等にも優れた硬化物が得られる。また、末端カルボキシル基を有するためアルカリ水溶液による現像も可能である。従って、本発明のカルボキシル基含有感光性樹脂を含有する光硬化性・熱硬化性組成物を用いることにより、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性等の諸特性に優れた硬化膜を低コストで生産性良く形成できる。
そのため、活性エネルギー線を用いて硬化させる紫外線硬化型印刷インキ用途等に使用可能であるほか、プリント配線板の製造時に使用されるソルダーレジスト、エッチングレジスト、メッキレジスト、層間絶縁材や、テープキャリアパッケージの製造に用いられる永久マスク、フレキシブル配線板用レジスト、カラーフィルター用レジスト等に有用である。また、本発明の光硬化性・熱硬化性組成物は、硬化後に反りが少ないため、フレキシブルプリント配線板やテープキャリアパッケージへの部品又はチップの装着が容易となり、また、従来使用されている液状ポリイミドインキと比較すると安価に生産可能である。
【図面の簡単な説明】
図１は、合成例１で得たカルボキシル基含有感光性樹脂の赤外吸収スペクトルである。
図２は、合成例３で得たカルボキシル基含有感光性樹脂の核磁気共鳴スペクトル（溶媒ＣＤＣｌ３、基準物質ＴＭＳ（テトラメチルシラン））である。
図３は、合成例３で得たカルボキシル基含有感光性樹脂の赤外吸収スペクトルである。
図４は、合成例４で得たカルボキシル基含有感光性樹脂の核磁気共鳴スペクトル（溶媒ＣＤＣｌ３、基準物質ＴＭＳ（テトラメチルシラン））である。
図５は、合成例４で得たカルボキシル基含有感光性樹脂の赤外吸収スペクトルである。Technical field
  The present invention relates to chain extension by addition reaction of alkylene oxide of novolak type phenol resin, followed byAcrylic acid and / or methacrylic acidThe light and / or thermosetting resin obtained by the addition of polybasic acid anhydride and more specifically, the cured product is excellent in heat resistance and toughness, and has high hardness and flexibility, Moreover, the present invention relates to a light and / or thermosetting resin that is rich in water resistance and chemical resistance.
  Furthermore, the present invention relates to a photocurable / thermosetting composition capable of alkali development and a cured product obtained therefrom, and more specifically, is used for the production of general printed wiring boards, flexible printed wiring boards, and tape carrier packages. Suitable for use as permanent masks, interlayer insulation layers of multilayer wiring boards, etc., after UV irradiation, images are formed by developing with dilute alkaline aqueous solution, heat treatment, or heat treatment after active energy ray irradiation, or heating Adhesion, solder heat resistance, moisture absorption resistance, PCT (pressure cooker) resistance, electroless gold plating resistance, bending resistance, folding resistance, flexibility, warpage by finishing and curing by irradiation with active energy rays after treatment , Liquid alkali developable photocurable / thermosetting composition capable of forming a cured film having excellent electrical insulation, and cured film thereof About.
Background art
  At present, some consumer printed wiring boards and most solder resists for industrial printed wiring boards, from the viewpoint of high accuracy and high density, form an image by developing after ultraviolet irradiation, and heat or light irradiation. A liquid development type solder resist that undergoes final curing (main curing) is used. In consideration of environmental problems, an alkali development type liquid solder resist using a dilute alkaline aqueous solution as a developing solution is mainly used. As an alkali development type solder resist using such a dilute alkaline aqueous solution, for example, Japanese Patent Application Laid-Open No. 61-243869 adds an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid. A solder resist composition composed of a photosensitive resin, a photopolymerization initiator, a diluent and an epoxy compound is disclosed in Japanese Patent Application Laid-Open No. 3-253093 in which a reaction product of a novolac epoxy compound and an unsaturated monobasic acid is acid-anhydrous. Japanese Patent Application Laid-Open No. 3-71137, Japanese Patent Application Laid-Open No. 3-250012, and a solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent, vinyl triazine or a mixture of vinyl triazine and dicyandiamide, and a melamine resin. The gazette states that epichlorohydrin is a reaction product of salicylaldehyde and monohydric phenol. Solder resist composed of photosensitive resin, photopolymerization initiator, organic solvent, etc. obtained by adding (meth) acrylic acid to the epoxy resin obtained by the reaction and further reacting with polybasic carboxylic acid or its anhydride. A composition is disclosed.
  As described above, several material systems have been proposed as solder resists and are currently used in large quantities in the production of actual printed wiring boards. However, solder resists are also required to have higher performance in response to the recent increase in the density of printed wiring boards as electronic devices become lighter, thinner and shorter. More recently, instead of IC packages such as QFP (Quad Flat Pack Package) and SOP (Small Outline Package) using a lead frame and sealing resin, printed wiring boards and seals with solder resist are used. An IC package using a stop resin has appeared. In these new packages, metal such as ball-shaped solder is arranged in one area on one side of the printed wiring board with solder resist, and the IC chip is directly connected to the other side with wire bonding or bumps, and sealed resin It has a sealed structure and is called by a name such as BGA (ball grid array), CSP (chip scale package) or the like. These packages have a larger number of pins and can be further reduced in size than packages of the same size such as QFP. Also in the mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and its introduction is progressing rapidly.
  However, a printed wiring board to which a commercially available alkali development type solder resist is applied is inferior in PCT resistance, which is a long-term reliability test of a package, and a cured product is peeled off. Further, the so-called popcorn phenomenon, in which moisture absorbed in the package during the reflow during package mounting due to moisture absorption of the solder resist boils and cracks occur in the solder resist film inside the package and its periphery, is regarded as a problem. Such problems of moisture absorption resistance and long-term reliability are not limited to the above-mentioned mounting technology, but are used for the manufacture of solder resists for general printed wiring boards, flexible printed wiring boards, and tape carrier packages. It is also undesirable in products for other applications such as solder resist and interlayer insulation layers of multilayer wiring boards such as build-up substrates.
  Thus, with the recent development of the electrical industry and the semiconductor industry, further improvement in characteristics, for example, improvement in heat resistance, toughness, flexibility, water resistance, and chemical resistance, is required and satisfied. Various new photosensitive resins have been developed.
  Conventionally, photosensitive resins starting from novolac epoxy resins have been widely used in many fields of electronic materials such as solder resists and etching resists because of their excellent adhesion, heat resistance, chemical resistance, and electrical insulation. It is used as a carboxyl group-containing photosensitive resin that is particularly excellent in heat resistance, and is obtained by reacting a polybasic acid anhydride with the reaction product of the cresol novolac epoxy resin and an unsaturated group-containing monocarboxylic acid. Resin (Japanese Patent Laid-Open No. 61-243869) is frequently used. However, although this resin is excellent in heat resistance, there is a problem that cracks due to heat shock are likely to occur because of large shrinkage upon curing, little elongation, and lack of toughness.
  As a photosensitive resin for solving this problem, a photosensitive prepolymer which is a reaction product of a resin obtained by partially epoxidizing a side chain hydroxyl group of a bisphenol type epoxy resin, (meth) acrylic acid and a polybasic acid anhydride (Japanese Patent Laid-Open No. Hei 9). -54434), an unsaturated group-containing polycarboxylic acid resin obtained by reacting a reaction product of cresol novolac type epoxy resin, acrylic acid and p-hydroxyphenethyl alcohol with tetrahydrophthalic anhydride (Japanese Patent Laid-Open No. 11-288091) ) Etc. have been proposed.
  However, these resins are still insufficient to satisfy both heat resistance and toughness.
  The present invention has been made in view of the above problems, and has good elongation, water resistance, chemical resistance, etc. in addition to balanced heat resistance and toughness, and good flexibility. It aims at providing the carboxyl group-containing photosensitive resin from which the hardened | cured material with this is obtained.
  Furthermore, the object of the present invention is required for solder resists of general printed wiring boards, solder resists used in the manufacture of flexible printed wiring boards and tape carrier packages, and interlayer insulating layers of multilayer wiring boards such as build-up boards. Maintain or improve properties such as adhesiveness, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, bending resistance, folding resistance, flexibility, warpage, and electrical insulation, and especially IC A cured film with excellent moisture absorption and PCT (pressure cooker) resistance required for the package can be obtained, and it can be used for high density and surface mounting of printed wiring boards, and can be developed in a liquid photocurability that can be developed with alkali. The object is to provide a thermosetting composition and a cured film obtained therefrom.
Disclosure of the invention
  In order to achieve the above object, according to one aspect of the present invention, a reaction product (c) of a novolac type phenol resin (a) and an alkylene oxide (b)Acrylic acid and / or methacrylic acidCarboxy group containing acid value obtained by reacting (d) and reacting the obtained reaction product (e) with polybasic acid anhydride (f) and having an acid value in the range of 30 to 150 mgKOH / g A photosensitive resin (A) is provided.
  According to a more specific preferred embodiment of the present inventionManyA carboxyl group-containing photosensitive resin (A) in which the basic acid anhydride (f) is an alicyclic dibasic acid anhydride is provided.
  The carboxyl group-containing photosensitive resin of the present invention is improved in flexibility and elongation by chain extension by addition reaction of alkylene oxide of novolak-type phenol resin, and has a terminal hydroxyl group generated by addition reaction of alkylene oxide.Acrylic acid and / or methacrylic acidSince the unsaturated group and carboxyl group are added to the end of the side chain by adding polybasic acid anhydride and adding polybasic acid anhydride, the reactivity is improved and heat resistance is achieved at a high level along with chain extension. Property and toughness are balanced, and a cured product having excellent hardness and flexibility, as well as excellent water resistance and chemical resistance can be obtained. Moreover, since it has a terminal carboxyl group, development with an aqueous alkaline solution is also possible.
  According to another aspect of the present invention, (A) a reaction product (c) of a novolak type phenol resin (a) and an alkylene oxide (b)Acrylic acid and / or methacrylic acidCarboxy group-containing photosensitive resin obtained by reacting (d) and reacting the obtained reaction product (e) with polybasic acid anhydride (f), (C) a photopolymerization initiator, and (D ) A photocurable / thermosetting composition capable of alkali development characterized by containing an epoxy resin, or (B) a photosensitive (meth) acrylate compound in addition to the above components. An alkali developable photocurable / thermosetting composition is provided.
  According to a preferred embodiment, there is provided an alkali-developable photocurable / thermosetting composition characterized by further containing (E) an organic solvent and / or (F) a curing catalyst in addition to the above-mentioned components. Is done.
  Furthermore, according to the other aspect of this invention, the hardened | cured material obtained from the said photocurable and thermosetting composition which can be developed is also provided. In a preferred embodiment, the composition is applied to a substrate, for example, a circuit-formed printed wiring board surface by a method such as a screen printing method, a roll coating method, a curtain coating method, or a spray coating method. Dry in an infrared drying oven, hot air drying oven, etc., and then irradiate active energy rays such as laser light directly according to the pattern or through a patterned photomask, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp Then, the active energy ray is irradiated using, for example, and then the unexposed portion is developed with an alkaline aqueous solution to form a predetermined pattern. Then, it is heat-treated, heat-treated after irradiation with active energy rays, or finish-cured (main-cured) by irradiation with active energy after heat treatment, thereby achieving adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless A cured film (cured product) excellent in various properties such as gold plating resistance, flex resistance, folding resistance, flexibility, warpage, and electrical insulation can be formed at low cost with high productivity.
BEST MODE FOR CARRYING OUT THE INVENTION
  As a result of intensive studies to solve the above-mentioned problems, the present inventors reacted an alkylene oxide adduct of a novolak type phenol resin with an unsaturated group-containing monocarboxylic acid, and obtained reaction product was polybasic. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride, particularly an unsaturated group-containing monocarboxylic acid is acrylic acid or / and methacrylic acid, and a polybasic acid anhydride is an alicyclic dibasic acid anhydride. A certain carboxyl group-containing photosensitive resin (A) is excellent in developability, photocurability and thermosetting property, and gives a cured product having both excellent heat resistance and toughness. The carboxyl group-containing photosensitive resin (A) In combination with a photopolymerization initiator (C) and an epoxy resin (D), or a photosensitive (meth) acrylate compound (B) in addition to these. Cured product obtained from the found to have excellent properties such as required Examples resist, which has led to the completion of the present invention.
  That is, the carboxyl group-containing photosensitive resin (A) of the present invention forms a main chain excellent in flexibility and elongation by chain extension by addition reaction of alkylene oxide of a novolak type phenol resin, and addition of alkylene oxide. To the terminal hydroxyl group produced by the reactionAcrylic acid and / or methacrylic acidAnd polybasic acid anhydrides are added, and unsaturated groups and carboxyl groups do not exist on the same side chain, and are located at the end of each side chain, so they have excellent reactivity and high heat resistance. It has toughness and excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain, and the resin is similar to an acid anhydride modified resin of epoxy acrylate used in the prior art. Therefore, a cured product having excellent water resistance and chemical resistance is obtained.
  Accordingly, the carboxyl group-containing photosensitive resin (A) is contained together with the photopolymerization initiator (C) and the epoxy resin (D), or in addition to these, a liquid containing the photosensitive (meth) acrylate compound (B). The photo-curing / thermosetting composition of the present invention exhibits excellent alkali developability, photo-curing property and thermosetting property, as well as adhesion, solder heat resistance, A cured product having excellent moisture absorption resistance, PCT resistance, electroless gold plating resistance, bending resistance, folding resistance, flexibility, warpage, and electrical insulation can be obtained.
  Hereinafter, each component of the carboxyl group-containing photosensitive resin of the present invention and the photocurable / thermosetting composition containing the same will be described in detail.
  First, as described above, the carboxyl group-containing photosensitive resin (A) of the present invention is converted into a reaction product (c) of a novolac type phenol resin (a) and an alkylene oxide (b).Acrylic acid And / or methacrylic acidIt is obtained by reacting (d) and reacting the obtained reaction product (e) with the polybasic acid anhydride (f). Each reaction is easily performed in a solvent or without a solvent using a catalyst as described below.
  Such a carboxyl group-containing photosensitive resin (A) desirably has an acid value in the range of 30 to 150 mgKOH / g, preferably 50 to 120 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin is lower than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 150 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.
  The novolak-type phenol resin (a) is obtained by a condensation reaction between phenols and formaldehyde, and these reactions are usually performed in the presence of an acidic catalyst.
  Examples of phenols include phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, and the like.
  The addition ratio of the alkylene oxide (b) to the novolac type phenol resin (a) is preferably 0.3 to 10.0 mol per equivalent of the phenolic hydroxyl group of the novolac type phenol resin (a). When the amount is less than 0.3 mol, the photocurability may be poor in the carboxy group-containing photosensitive resin. Moreover, when more than 10.0 mol, there exists a possibility that thermosetting property may become scarce.
  The addition reaction of the alkylene oxide (b) to the novolak-type phenol resin (a) is, for example, an alkali metal compound such as sodium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or the like. In the presence of a quaternary basic salt compound or a mixture of an alkali metal compound and a quaternary basic salt compound, for example, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate such as tate, ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, and mixed solvents thereof, 80 to 180 ° C., normal pressure -10kg / cm2Is done. In particular, a solvent in which ketones and aromatic hydrocarbons are used alone or in combination of two or more is preferably used.
  Examples of the alkylene oxide (b) include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.
  A reaction product (c) of the novolac phenolic resin (a) and an alkylene oxide (b);Acrylic acid and / or methacrylic acidThe reaction temperature in the esterification reaction with (d) is preferably about 50 to 150 ° C., and the reaction can be carried out under reduced pressure, normal pressure, or increased pressure. Reaction solvents include n-hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, trichloroethane, tetrachloroethylene, methyl chloroform, diisopropyl ether, and ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate. Acetic esters such as diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate are preferably used. These solvents can be used alone or in admixture of two or more. As the esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin and the like are appropriately used. The esterification reaction is preferably performed in the presence of a polymerization inhibitor, and hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like are preferably used as the polymerization inhibitor.
  Unsaturated monocarboxylic acidAs the lightAcrylic acid and / or methacrylic acid are preferred because of their effects on reactivity and physical properties of cured products, especially heat resistance, moisture absorption resistance and electrical properties.SimpleIt can be used alone or in admixture of two or more.
  The reaction product (c) andAcrylic acid and / or methacrylic acidThe reaction product (e) of (d) is reacted with the polybasic acid anhydride (f) to obtain the carboxyl group-containing photosensitive resin (photosensitive prepolymer) of the present invention. The amount of the acid anhydride (f) used is such that the acid value of the resulting carboxyl group-containing photosensitive resin (A) is preferably 30 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g. To do. The reaction is usually carried out at about 50 to 150 ° C. in the presence or absence of an organic solvent described later in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine are added as a catalyst. May be.
  Examples of the polybasic acid anhydride (f) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Cycloaliphatic dibasic anhydrides such as methylendomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, anhydrous Aliphatic or aromatic dibasic acid anhydrides such as trimellitic acid, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic anhydride, benzofu Aliphatic or aromatic tetrabasic acid dianhydride, such as non-tetracarboxylic acid dianhydride and the like, can be used one or two or more of these. Among these, alicyclic dibasic acid anhydrides are particularly preferable.
  In addition, other carboxyl group-containing photosensitive resins, for example, photosensitive resins obtained by adding an acid anhydride to a reaction product of a novolak-type and / or bisphenol-type epoxy compound and an unsaturated monobasic acid are used for the purpose of improving characteristics. It can be mixed with the carboxyl group-containing photosensitive resin of the present invention.
  As the photosensitive (meth) acrylate compound (B), a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule at room temperature can be used. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the composition. The photosensitive (meth) acrylate compound that is liquid at room temperature is used for the purpose of increasing the photoreactivity of the composition, as well as adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an aqueous alkali solution. Also fulfills. However, if a large amount of liquid photosensitive (meth) acrylate compound is used at room temperature, the dryness of the coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. It is not preferable. The compounding amount of the photosensitive (meth) acrylate compound (B) is preferably 50 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A) (the same applies hereinafter as the solid content).
  Examples of the photosensitive (meth) acrylate compound (B) include hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; polyethylene glycol diacrylate Water-soluble acrylates such as polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; trimethylolpropane, hydrogenated bisphenol A, etc. Polyfunctional alcohol or polyhydric phenol ethylene oxide such as bisphenol A and biphenol Acrylates of adducts and / or propylene oxide adducts; polyfunctional or monofunctional polyurethane acrylates which are isocyanate modified products of the above hydroxyl group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resins Examples thereof include epoxy acrylates which are (meth) acrylic acid adducts, and methacrylates corresponding to the above acrylates, and these can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable.
  Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethyl Aminoacetophenones such as amino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloro Ant Anthraquinones such as laquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoylper Organic peroxides such as oxide and cumene peroxide; thiols such as 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Compound; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone; benzophenone, 4,4'-bisdiethyl Benzophenones or xanthones such as amino benzophenone; and 2,4,6-trimethylbenzoyl diphenylphosphine oxide. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added. A titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane. -1-one and the like, but is not particularly limited to these, as long as it absorbs light in the ultraviolet or visible light region and radically polymerizes an unsaturated group such as a (meth) acryloyl group. The polymerization initiator and the photoinitiator aid are not limited and can be used alone or in combination. And the usage-amount is the ratio of 0.5-25 mass parts with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A).
  Specific examples of the epoxy resin (D) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 840, Epicron 850 manufactured by Dainippon Ink & Chemicals, Inc. Epicron 1050, Epicron 2055, Etototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names); manufactured by Japan Epoxy Resin Co., Ltd. Epicort YL903, Daikoku Ink Chemical Co., Ltd. Epicron 152, Epicron 165, Toto Kasei Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. E. R. 542, Brominated epoxy resins such as Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; Epicoat 152, Epicoat 154, Dow Chemical (manufactured by Japan Epoxy Resin Co., Ltd.) D. manufactured by Co., Ltd. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Novolak type epoxy such as EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220 (all trade names) manufactured by Sumitomo Chemical Co., Ltd. Resins; Bisphenols such as Epiklon 830 manufactured by Dainippon Ink & Chemicals, Ltd., Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. (all trade names) F-type epoxy resin; Epototo ST-2004, ST-2 manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 07, ST-3000 (all are trade names); Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resins such as Sumi-Epoxy ELM-120 (all trade names) manufactured by Daicel Chemical Industries Ltd. Alicyclic epoxy resins such as Celoxide 2021 (trade names) manufactured by Daicel Chemical Industries, Ltd .; Japan Epoxy Resins Co., Ltd. YL-933 manufactured by Nippon Kayaku Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., trihydroxyphenylmethane type epoxy resin such as EPPN-502 (both trade names); YL-6056 manufactured by Japan Epoxy Resin Co., Ltd., YX -4000, YL-6121 (both trade names) and other bixylenol type or biphenol type epoxy resins or EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals Co., Ltd. (all trade names), etc. Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin Co .; Tetraphenylol such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Ethane type epoxy resin; heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT (trade name) manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 (trade name) manufactured by Nippon Steel Chemical Co., Ltd .; ESN-190, ESN- manufactured by Nippon Steel Chemical Co., Ltd. 360, Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink & Chemicals, Inc .; HP-7200 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H (all trade names); Glycidyl methacrylate copolymer epoxy such as CP-50S and CP-50M (all trade names) manufactured by NOF Corporation Resins; Furthermore, hydantoin type epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and the like, are not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a biphenol type or bixylenol type epoxy resin or a mixture thereof is particularly preferable.
  The epoxy resin (D) as described above improves properties such as adhesion and heat resistance of the resist by thermosetting. The compounding quantity is sufficient with the ratio of 10 mass parts or more and 70 mass parts or less with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A), Preferably it is a ratio of 15-60 mass parts. When the compounding quantity of an epoxy resin (D) is less than the said range, the hygroscopic property of a cured film becomes high and PCT tolerance tends to fall, or the heat resistance and electroless-plating-proof property which are easy to fall also become low. On the other hand, when the above range is exceeded, the developability of the coating film and the electroless plating resistance of the cured film are deteriorated, and the PCT resistance is also inferior.
  Moreover, the photocurable / thermosetting composition of the present invention dissolves the carboxyl group-containing photosensitive resin (A) and the photosensitive (meth) acrylate compound (B), and is suitable for a coating method. In order to adjust to a viscosity, an organic solvent (E) can be mix | blended. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more. In addition, the compounding quantity of an organic solvent can be made into the arbitrary quantity according to the coating method.
  Furthermore, the photocurable / thermosetting composition of the present invention preferably contains a curing catalyst (F) in order to improve its thermosetting properties. Examples of the curing catalyst (F) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine, and the like can be used. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503X manufactured by San Apro Co., Ltd. U-CAT3502X (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and any catalyst that cures the epoxy resin or promotes the reaction between the epoxy group and the carboxyl group may be used alone or in admixture of two or more. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, These compounds are preferably used in combination with the curing catalyst. The amount of the curing catalyst to be blended is a normal quantitative ratio, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts per 100 parts by weight of the carboxyl group-containing photosensitive resin (A). The ratio is 0 part by mass.
  The photocurable / thermosetting composition of the present invention may further include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, and spherical silica as necessary. , Talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and other known and commonly used inorganic fillers may be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The blending amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass per 100 parts by mass of the carboxyl group-containing photosensitive resin (A).
  The composition of the present invention may further comprise known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone monomethyl as necessary. Known and conventional thermal polymerization inhibitors such as ether, t-butylcatechol, pyrogallol and phenothiazine, known and commonly used thickeners such as fine silica, organic bentonite and montmorillonite, silicone-based, fluorine-based and polymer-based antifoaming agents And / or known additives such as leveling agents, silane coupling agents such as imidazole, thiazole, and triazole can be blended.
  The photocurable / thermosetting composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method, and this is applied to, for example, a printed wiring board formed with a circuit. It is applied by a screen printing method, curtain coating method, spray coating method, roll coating method, etc., and tack-free coating is performed by evaporating and drying an organic solvent contained in the composition at a temperature of about 60 to 100 ° C., for example. A film can be formed. Thereafter, active energy rays such as laser light are directly irradiated according to the pattern, or selectively exposed with active energy rays through a photomask on which the pattern is formed, and the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. Furthermore, adhesion, solder heat resistance, moisture absorption resistance, PCT can be achieved by heat curing only, or heat curing after irradiation with active energy rays or final curing (main curing) by irradiation with active energy rays after heat curing. A cured film (cured product) excellent in resistance, electroless gold plating resistance, bending resistance, folding resistance, flexibility, warpage, and electrical insulation is formed.
  As the alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
  As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, laser beams and the like can also be used as active energy rays.
  Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited to these examples. In the following description, “part” means part by mass unless otherwise specified.
Preparation of carboxyl group-containing photosensitive resin
Synthesis example 1
  In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 109 parts of Novolak-type cresol resin (trade name “Resitop PSF-2803”, OH equivalent: 109) manufactured by Gunei Chemical Industry Co., Ltd. , 2.6 parts of 50% aqueous sodium hydroxide solution and 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were charged, and the system was purged with nitrogen while stirring, then heated to 150 ° C., 8kg / cm2Then, 60 parts of propylene oxide was gradually introduced and reacted. Reaction is gauge pressure 0.0kg / cm2The reaction was continued for about 4 hours until it became, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator. The hydroxyl value was 167 g / eq. Thus, an alkylene oxide adduct of a novolac cresol resin was obtained. This was an average of 1 mole of alkylene oxide added per equivalent of phenolic hydroxyl group.
  122 parts of alkylene oxide adduct of the obtained novolac-type cresol resin, 34 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether, 100 parts of toluene were stirred, a thermometer, and air blown The reactor was equipped with a tube, stirred while blowing air, and reacted at 110 ° C. for 6 hours. After the water produced by the reaction began to distill as an azeotrope with toluene, the reaction was continued for an additional 5 hours and cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and diethylene glycol monoethyl ether acetate was added to obtain a novolak acrylate resin solution having a nonvolatile content of 60%.
  Next, a four-necked flask equipped with a stirrer and a reflux condenser was charged with 170 parts of the resulting novolak acrylate resin solution, 0.05 part of hydroquinone monomethyl ether, and 0.2 part of pyridine, and this mixture was heated to 120 ° C. Then, 23 parts of tetrahydrophthalic anhydride was added, reacted for 6 hours, cooled, and then taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 64% and a solid content acid value of 67 mgKOH / g. Hereinafter, this reaction solution is referred to as A-1 varnish. The infrared absorption spectrum (IR spectrum) of the obtained carboxyl group-containing photosensitive resin is shown in FIG.
Synthesis example 2
  The hydroxyl value obtained in the same manner as in Synthesis Example 1 was 167 g / eq. 122 parts of alkylene oxide adduct of novolac type cresol resin, 26 parts of acrylic acid, 2.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether, 100 parts of toluene, a stirrer, thermometer, air blowing tube The reactor was prepared, stirred while blowing air, and reacted at 110 ° C. for 6 hours. After the water produced by the reaction began to distill as an azeotrope with toluene, the reaction was continued for an additional 5 hours and cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and diethylene glycol monoethyl ether acetate was added to obtain a novolak acrylate resin solution having a nonvolatile content of 61%.
  Next, a four-necked flask equipped with a stirrer and a reflux condenser was charged with 179 parts of the obtained novolak acrylate resin solution, 0.05 part of hydroquinone monomethyl ether, and 0.35 part of pyridine, and this mixture was heated to 120 ° C. Then, 41.3 parts of tetrahydrophthalic anhydride was added, allowed to react for 6 hours, cooled and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 68% and a solid content acid value of 100 mgKOH / g. Hereinafter, this reaction solution is referred to as A-2 varnish.
Synthesis example 3
  119.4 parts of Novolac cresol resin (trade name “Shonol CRG951”, OH equivalent: 119.4) manufactured by Showa Polymer Co., Ltd.) in an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device Then, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased. Next, 63.8 parts of propylene oxide was gradually added dropwise to 125-132 ° C., 0-4.8 kg / cm.2For 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of about 1.08 mole of alkylene oxide added per equivalent of phenolic hydroxyl group.
  293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone, and 252.9 parts of toluene were stirred and a thermometer. The reactor was equipped with an air blowing tube, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 70.6% and a solid content acid value of 87.7 mgKOH / g. Hereinafter, this resin solution is referred to as A-3 varnish. Of the obtained carboxyl group-containing photosensitive resin1The H-NMR spectrum is shown in FIG. 2, and the IR spectrum is shown in FIG.
Synthesis example 4
  In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 109 parts of novolak-type cresol resin (trade name “Resitop PSF-2803”, OH equivalent: 109) manufactured by Gunei Chemical Industry Co., Ltd. Then, 1.09 parts of potassium hydroxide and 109 parts of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 348 parts of propylene oxide is gradually added dropwise to 125 to 132 ° C. and 0 to 4.8 kg / cm.2For 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.2 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 84.3% and the hydroxyl value was 444.8 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 5.79 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
  542.1 parts of the obtained novolak-type cresol resin alkylene oxide reaction solution, 36 parts of acrylic acid, 9 parts of methanesulfonic acid, 0.2 part of methylhydroquinone, and 382 parts of toluene were equipped with a stirrer, thermometer and air blowing tube. The reactor was charged, air was blown at a rate of 10 ml / min, and the mixture was reacted at 110 ° C. for 12 hours while stirring. 7.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 26 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 340 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution having a nonvolatile content of 58%.
  Next, 418.5 parts of the obtained novolak acrylate resin solution and 0.76 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 38 parts of tetrahydrophthalic anhydride was gradually added, reacted at 107 to 119 ° C. for 3 hours, cooled and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 63.8% and a solid content acid value of 59.9 mgKOH / g. Hereinafter, this resin solution is referred to as A-4 varnish. Of the obtained carboxyl group-containing photosensitive resin1The H-NMR spectrum is shown in FIG. 4, and the IR spectrum is shown in FIG.
Synthesis example 5
  In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 150 parts of Novolak cresol resin (trade name “Resitop PSF-2803”, OH equivalent: 109) manufactured by Gunei Chemical Industry Co., Ltd. Then, 3.0 parts of 50% aqueous sodium hydroxide solution and 150 parts of ethylene glycol monoethyl ether acetate were added, the inside of the system was purged with nitrogen while stirring, then heated to 150 ° C., 8 kg / cm2Then, 56 parts of propylene oxide was gradually introduced and reacted. Reaction is gauge pressure 0.0kg / cm2The reaction was continued for about 4 hours until it became, and then cooled to room temperature. To this reaction solution, 3.8 parts of 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. The neutralized reaction product is diluted with toluene, washed with water three times, desolvated with an evaporator, diethylene glycol monoethyl ether acetate is added, the non-volatile content is 80%, and the hydroxyl value in terms of solid content is 149 g / eq. An alkylene oxide adduct of a novolac-type cresol resin was obtained. This was an average of 0.7 mole of alkylene oxide added per equivalent of phenolic hydroxyl group.
  187 parts of an alkylene oxide adduct of the obtained novolac-type cresol resin, 25 parts of acrylic acid, 2.0 parts of p-toluenesulfonic acid, 0.02 part of hydroquinone monomethyl ether, and 70 parts of toluene were mixed with a stirrer, thermometer, and air blown. A reactor equipped with a tube was charged, air was blown at a rate of 50 ml / min, and the reaction was carried out at 110 ° C. for 5 hours while stirring. After water produced by the reaction began to distill as an azeotrope with toluene, the reaction was further continued for 5 hours. The obtained reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and diethylene glycol monoethyl ether acetate was added to obtain a novolak acrylate resin solution having a nonvolatile content of 55%.
  Next, 238 parts of the resulting novolak acrylate resin solution, 0.02 part of hydroquinone monomethyl ether, and 1.3 parts of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser. It heated at 120 degreeC, 39 parts of tetrahydrophthalic anhydride was added, it was made to react for 6 hours, and it took out after cooling. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 61% and a solid content acid value of 83 mgKOH / g. Hereinafter, this reaction solution is referred to as A-5 varnish.
Comparative Synthesis Example 1
  Cresol novolac type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent: 220) 220 parts was placed in a four-necked flask equipped with a stirrer and reflux condenser, and carbitol acetate 220 parts. Was added and dissolved by heating. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction product was taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 64% and a solid acid value of 97 mgKOH / g. Hereinafter, this reaction solution is referred to as B-1 varnish.
Comparative Synthesis Example 2
  220 parts of ECON-104S of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 220 parts of carbitol acetate was added, Dissolved by heating. Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95-105 ° C., 50.4 parts of acrylic acid and 41.5 parts of p-hydroxyphenethyl alcohol were gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 116 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction product was taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 66% and a solid acid value of 98 mgKOH / g. Hereinafter, this reaction solution is referred to as B-2 varnish.
Comparative Synthesis Example 3
  A flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer was charged with 313 parts of bisphenol A and 987 parts of bisphenol A type epoxy resin (Epiclon-840, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent: 180). The solution was dissolved at 120 ° C. with stirring under a nitrogen atmosphere. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C., the reaction was continued for about 90 minutes while maintaining the temperature at 150 ° C., and an epoxy equivalent of 475 g / eq. An epoxy compound was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 1851 parts of epichlorohydrin and 1690 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 110 parts of 96% sodium hydroxide was added in portions over 90 minutes, followed by further reaction for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled at 120 ° C. under reduced pressure of 50 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer, and an epoxy equivalent of 336 g / eq. The polynuclear epoxy compound was obtained. Next, 336 parts of the above polynuclear epoxy compound is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 300 parts of carbitol acetate is added and dissolved by heating, 0.46 part of methylhydroquinone, 1. 38 parts were added and heated to 95-105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 152 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and a solid acid value of 98 mgKOH / g. Hereinafter, this reaction solution is referred to as B-3 varnish.
Preparation of photocurable and thermosetting resin composition
Composition Examples 1-5 and Comparative Composition Examples 1-3
  The compounding components shown in Table 1 using each varnish obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 were kneaded with a three-roll mill to obtain a photocurable / thermosetting resin composition. . Table 2 shows the characteristic values of each composition.
[Table 1]
Figure 0003964326
[Table 2]
Figure 0003964326
  The evaluation method of the performance test in Table 2 is as follows.
(1) Glass transition point
  The compositions of the above composition examples and comparative composition examples were applied to a Teflon plate that had been washed and dried in advance by a screen printing method, and dried at 80 ° C. for 40 minutes in a hot-air circulating drying furnace. After cooling this to room temperature, the exposure amount is 1000 mJ / cm.2Then, the film was exposed to the following conditions and cured in a hot air circulating drying oven at 150 ° C. for 60 minutes. After cooling this to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.
(2) Tensile modulus, (3) Tensile strength (tensile fracture strength), (4) Elongation rate (tensile fracture elongation)
  The tensile elasticity modulus, tensile strength (tensile fracture strength), and elongation rate (tensile fracture elongation) of the above evaluation samples were measured with a tension-compression tester (manufactured by Shimadzu Corporation).
  The compositions of the above composition examples and comparative composition examples were applied to a Kapton material (thickness 25 μm) that had been washed and dried in advance by screen printing, and dried at 80 ° C. for 40 minutes in a hot air circulating drying furnace. After cooling this to room temperature, the exposure amount is 1000 mJ / cm.2Then, the film was exposed to the following conditions and cured in a hot-air circulating drying oven at 150 ° C. for 60 minutes to obtain evaluation samples for folding resistance test and flexibility test.
(5) Folding resistance
  The cured film was bent outward by 180 ° and evaluated according to the following criteria.
  ○: No crack in the cured film
  Δ: The cured film has some cracks
  X: The cured film has cracks
(6) Flexibility
  By placing one side of a film-shaped test piece prepared by processing the cured film into a width of 10 mm and a length of 90 mm on an electronic balance and bending the other side, an electronic balance is obtained until the distance between the films reaches 3 mm. The maximum load applied to was evaluated as the repulsive force according to the following criteria.
  ○: Less than 10 g
  Δ: Less than 10-30 g
  X: 30 g or more
(7) Water absorption rate
  The compositions of the above composition examples and comparative composition examples were applied to a glass plate whose weight had been measured in advance by a screen printing method, and dried at 80 ° C. for 40 minutes in a hot air circulation drying oven. After cooling this to room temperature, the exposure amount is 1000 mJ / cm.2Then, the film was exposed to the following conditions and cured in a hot-air circulating drying furnace at 150 ° C. for 60 minutes to obtain an evaluation sample. After cooling this to room temperature, the weight of the evaluation sample was measured. Next, this evaluation sample was measured at 121 ° C. and 100% R.D. using a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412MD). H. Then, the weight of the cured product after the treatment was measured, and the water absorption rate of the cured product was determined by the following formula.
  Water absorption rate = {(W2-W1) / (W1-Wg)} × 100
  Where W1Is the weight of the evaluation sample, W2Is the weight of the evaluation sample after PCT treatment, WgIs the weight of the glass plate.
(8) Pencil hardness: determined in accordance with JIS K 5400.
  The compositions of the above composition examples and comparative composition examples were applied to a printed wiring board that had been washed with water and dried in advance by a screen printing method, and dried at 80 ° C. for 40 minutes in a hot air circulation type drying furnace. After cooling this to room temperature, the exposure amount is 1000 mJ / cm.2The film was exposed to the following conditions and cured in a hot air circulating drying oven at 150 ° C. for 60 minutes to obtain an evaluation substrate for acid resistance test, alkali resistance test and heat resistance test.
(9) Acid resistance test
  The evaluation substrate was taken out after being immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, and the state and adhesion of the coating film were comprehensively evaluated. The judgment criteria are as follows.
  ○: No change
  Δ: Slightly changing
  X: The coating film has blisters or swelling drops
(10) Alkali resistance test
  The evaluation substrate was tested and evaluated in the same manner as in the acid resistance test, except that the 10 vol% sulfuric acid aqueous solution was changed to a 10 vol% sodium hydroxide aqueous solution.
(11) Heat resistance
  After leaving the evaluation substrate in a hot air circulating drying oven at 150 ° C. for 24 hours, a 10 × 10 (100 square) grid is made in accordance with JIS K 5600-5-6, and heat resistance is achieved by adhesion by tape peeling. Degradability was tested and evaluated. The judgment criteria are as follows.
  ○: 100/100 (not peeled off at all)
  Δ: 99/100 to 70/100 (slight peeling occurred)
  X: 69/100-(remarkably peeled off)
  As is apparent from the results shown in Table 2, the cured product of the composition obtained using the carboxyl group-containing photosensitive resin of the present invention is excellent in heat resistance and toughness (tensile elasticity, tensile strength), stretched, It has excellent properties such as flexibility (folding resistance, flexibility), water absorption, hardness, and chemical resistance. On the other hand, the cured product of the composition obtained using the carboxyl group-containing photosensitive resin of the comparative example has tensile strength, flexibility (folding resistance, flexibility), elongation, moisture resistance (water absorption). Was inferior.
Composition Examples 6-10, Comparative Composition Examples 4-6
  Each component was blended according to the blending composition shown in Table 3, and separately kneaded with a three-roll mill to prepare a photocurable / thermosetting composition.
[Table 3]
Figure 0003964326
  The photocurable / thermosetting compositions of Composition Examples 6 to 10 and Comparative Composition Examples 4 to 6 are patterned by screen printing so that the thickness is 20 to 30 μm using a 100 mesh polyester screen. The entire surface of the copper through-hole printed wiring board is applied, and the coating is dried in a hot air circulation drying oven at 80 ° C. for a predetermined time. A negative film having a resist pattern is adhered to the coating, and an ultraviolet exposure device ( Using an Oak Seisakusho Co., Ltd. model HMW-680GW), ultraviolet rays were irradiated (exposure amount 350 mJ / cm).2). Then, 2.0 kg / cm for 60 seconds with 1% aqueous sodium carbonate solution2The unexposed portion was dissolved and removed by developing at a spray pressure of. Then, heat curing was performed for 60 minutes in a hot air circulation drying oven at 150 ° C., and each test of adhesion, solder heat resistance, PCT resistance, and electroless gold plating resistance was performed on the test piece having the obtained cured film. . The test method and evaluation method are as follows.
(12) Developability:
  With respect to the drying time of 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, or 90 minutes, the state after exposure and development was visually determined with a magnifier. The results are shown in Table 4.
  ○: During development, the coating film was completely removed and development was possible.
  X: At the time of development, even a little residue remained, and there was a portion that was not developed.
[Table 4]
Figure 0003964326
(13) Adhesion:
  According to the test method of JIS D 0202, the cured film was cross-cut in a grid pattern, and then the peeled state after the peeling test with a cellophane adhesive tape was visually determined. The results are shown in Table 5. The test piece that could not be developed was not evaluated.
  A: 100/100 with no peeling
  ○: 100/100 with the crosscut part peeled off a little
  Δ: 50/100 to 90/100
  X: 0/100 to 50/100
[Table 5]
Figure 0003964326
(14) Solder heat resistance:
  According to the test method of JIS C 6481, the test piece was immersed in a 260 ° C. solder bath for 10 seconds three times, and the change in appearance was evaluated according to the following criteria. The results are shown in Table 6. Note that the test pieces that could not be developed were not evaluated. Moreover, as a post flux (rosin type), a flux according to JIS C 6481 was used.
  ○: No change in appearance
  Δ: Discoloration of the cured film is observed
  ×: Hardened film floated, peeled off, solder dipped
[Table 6]
Figure 0003964326
(15) Water absorption:
  A cured film is formed on a ceramic substrate (alumina substrate) whose mass has been measured in advance under the above conditions with a drying time of 40 minutes, and the total mass is measured. And after immersing this in 22 degreeC ion-exchange water for 24 hours, mass was measured and the increase rate of mass was made into the water absorption. The results are shown in Table 7.
[Table 7]
Figure 0003964326
(16) PCT resistance:
  The PCT resistance of the cured film was evaluated according to the following criteria under the conditions of 121 ° C. and saturation of 50 hours. The results are shown in Table 8. Note that the test pieces that could not be developed were not evaluated.
  ○: The cured film does not blister, peel off or discolor.
  Δ: The cured film has some swelling, peeling, and discoloration.
  X: The cured film has blistering, peeling and discoloration.
[Table 8]
Figure 0003964326
(17) Electroless gold plating resistance:
  The copper surface of the patterned copper through-hole printed wiring board is subjected to surface treatment (surface polishing (Ishii Notation Co., Ltd., No. 1200 after roll-shaped buff polishing, Ishii Notation Co., Ltd., Abrasive No. 270, jet scrub polishing, washed with water and dried.) In the same manner as described above, coating, drying, exposure, development, and heating were performed to obtain a test piece. Using this test piece, electroless gold plating was performed as in the following steps, and the test piece was subjected to a change in appearance and a peeling test using a cellophane adhesive tape to determine the peeled state of the cured film. The results are shown in Table 9. A test piece that could not be developed was not evaluated.
  ○: No change in appearance and no peeling of the cured film.
  (Triangle | delta): Although there is no change of an external appearance, there exists slight peeling in a cured film.
  X: Lifting of the cured film is observed, plating stagnation is observed, and peeling of the cured film is large in the peeling test.
  Electroless gold plating process:
  1. Degreasing: The test piece was immersed in an acidic degreasing solution at 30 ° C. (manufactured by Nippon McDermid Co., Ltd., 20% Vol aqueous solution of Metex L-5B) for 3 minutes.
  2. Water washing: Immerse the test piece in running water for 3 minutes.
  3. Soft etch: 14.3% wt, immersed in an aqueous solution of ammonium persulfate for 3 minutes at room temperature.
  4). Water washing: Immerse the test piece in running water for 3 minutes.
  5. Acid immersion: 10% Vol. The test piece is immersed in an aqueous sulfuric acid solution at room temperature for 1 minute.
  6). Rinsing: Immerse the test piece in running water for 30 seconds to 1 minute.
  7. Application of catalyst: The test piece was immersed in a 30 ° C. catalyst solution (manufactured by Meltex, 10% Vol. Aqueous solution of metal plate activator 350) for 7 minutes.
  8). Water washing: Immerse the test piece in running water for 3 minutes.
  9. Electroless nickel plating: The test piece was immersed in a nickel plating solution of 85 ° C. and pH = 4.6 (manufactured by Meltex, Melplate Ni-865M, 20% Vol. Aqueous solution) for 20 minutes.
  10. Acid immersion: 10% Vol. The test piece is immersed in an aqueous sulfuric acid solution at room temperature for 1 minute.
  11. Water washing: Immerse the test piece in running water, 30 seconds to 1 minute.
  12 Electroless gold plating: The test piece was immersed in a gold plating solution of 95 ° C. and pH = 6 (manufactured by Meltex Co., Ltd., Aurolectroles UP 15% Vol. Potassium gold cyanide 3% Vol. Aqueous solution) for 10 minutes.
  13. Water washing: Immerse the test piece in running water for 3 minutes.
  14 Hot water washing: Immerse the test piece in warm water of 60 ° C., wash thoroughly with water for 3 minutes, thoroughly drain water, and dry to obtain an electroless gold-plated test piece.
[Table 9]
Figure 0003964326
  A kapton material (thickness 25 μm) is used in place of the patterned copper through-hole printed wiring board, and the photo-curing / thermosetting composition is applied and cured by the above-described method, thereby providing bending resistance and resistance. Tests were performed for foldability, flexibility, and warpage.
(18) Bending resistance:
  According to IPC-SM-840B TM2.4.29, evaluation was performed according to the following criteria under the condition of 1/8 inch diameter and 10 cycles. The results are shown in Table 10. Note that the test pieces that could not be developed were not evaluated.
  ○: No crack in the cured film
  Δ: The cured film has some cracks
  X: The cured film has cracks
[Table 10]
Figure 0003964326
(19) Folding resistance:
  The cured film was bent outward by 180 ° and evaluated according to the following criteria. The results are shown in Table 11. Note that the test pieces that could not be developed were not evaluated.
  ○: No crack in the cured film
  Δ: The cured film has some cracks
  X: The cured film has cracks
[Table 11]
Figure 0003964326
(20) Flexibility:
  Evaluation was performed by the same method and standard as in the above (6) flexibility test. The results are shown in Table 12. Note that the test pieces that could not be developed were not evaluated.
[Table 12]
Figure 0003964326
(21) Warpage:
  The cured film was processed to 150 × 110 mm, the average of the heights of the four corners from the bottom (hereinafter referred to as the four-corner average value) was measured and calculated, and the warpage was evaluated according to the following criteria. The results are shown in Table 13. Note that the test pieces that could not be developed were not evaluated.
  ○: The square average value is less than 6 mm
  Δ: Four-square average value of 6 mm or more and less than 12 mm
  ×: The square average value is 12 mm or more or rounded and cannot be measured.
[Table 13]
Figure 0003964326
(22) Electrical insulation:
  Instead of the patterned copper through-hole printed wiring board, the B pattern of the printed circuit board (thickness 1.6 mm) defined by IPC is used, and the photocurable / thermosetting composition is formed by the above method. The coating was cured and the electrical insulation of the resulting cured film was evaluated according to the following criteria.
  Humidification conditions: temperature 85 ° C., humidity 85% RH, applied voltage 100 V, 500 hours.
  Measurement conditions: measurement time 60 seconds, applied voltage 500V.
  The results are shown in Table 14. Note that the test pieces that could not be developed were not evaluated.
  ○: Insulation resistance value after humidification 109Ω or more, no copper migration.
  Δ: Insulation resistance value after humidification 109Ω or more, copper migration.
  X: Insulation resistance value after humidification 108Less than Ω, copper migration.
[Table 14]
Figure 0003964326
Industrial applicability
  As described above, the carboxyl group-containing photosensitive resin of the present invention is improved in flexibility and elongation by chain extension by addition reaction of alkylene oxide of novolak-type phenol resin, and terminal hydroxyl group generated by addition reaction of alkylene oxide. By adding an unsaturated group-containing monocarboxylic acid and polybasic acid anhydride, an unsaturated group or a carboxyl group is added to the end of the side chain. Combined with extension, heat resistance and toughness are balanced at a high level, and a cured product having excellent hardness and flexibility as well as water resistance and chemical resistance can be obtained. Moreover, since it has a terminal carboxyl group, development with an aqueous alkaline solution is also possible. Therefore, by using the photocurable / thermosetting composition containing the carboxyl group-containing photosensitive resin of the present invention, adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, bending resistance A cured film having excellent properties such as property, folding resistance, flexibility, warpage, and electrical insulation can be formed at low cost and with high productivity.
  Therefore, it can be used for UV curable printing inks that are cured using active energy rays, as well as solder resists, etching resists, plating resists, interlayer insulation materials, tape carrier packages used in the production of printed wiring boards. It is useful for permanent masks, flexible wiring board resists, color filter resists, and the like used in the production of the above. In addition, since the photocurable / thermosetting composition of the present invention has less warping after curing, it is easy to attach components or chips to a flexible printed wiring board or a tape carrier package, and a conventionally used liquid is also used. Compared to polyimide ink, it can be produced at low cost.
[Brief description of the drawings]
  1 is an infrared absorption spectrum of the carboxyl group-containing photosensitive resin obtained in Synthesis Example 1. FIG.
  FIG. 2 shows the nuclear magnetic resonance spectrum (solvent CDCl) of the carboxyl group-containing photosensitive resin obtained in Synthesis Example 3.3Reference material TMS (tetramethylsilane)).
  FIG. 3 is an infrared absorption spectrum of the carboxyl group-containing photosensitive resin obtained in Synthesis Example 3.
  FIG. 4 shows the nuclear magnetic resonance spectrum (solvent CDCl) of the carboxyl group-containing photosensitive resin obtained in Synthesis Example 4.3Reference material TMS (tetramethylsilane)).
  FIG. 5 is an infrared absorption spectrum of the carboxyl group-containing photosensitive resin obtained in Synthesis Example 4.

Claims (13)

ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られ、３０〜１５０ｍｇＫＯＨ／ｇの範囲内にある酸価を有するカルボキシル基含有感光性樹脂。The reaction product (c) of the novolak type phenol resin (a) and the alkylene oxide (b) is reacted with acrylic acid and / or methacrylic acid (d), and the resulting reaction product (e) and the polybasic acid anhydride are reacted. A carboxyl group-containing photosensitive resin obtained by reacting the product (f) and having an acid value in the range of 30 to 150 mgKOH / g. 多塩基酸無水物（ｆ）が脂環式二塩基酸無水物である請求項１に記載のカルボキシル基含有感光性樹脂。  The carboxyl group-containing photosensitive resin according to claim 1, wherein the polybasic acid anhydride (f) is an alicyclic dibasic acid anhydride. ノボラック型フェノール樹脂（ａ）に対するアルキレンオキシド（ｂ）の付加割合は、ノボラック型フェノール樹脂（ａ）のフェノール性水酸基１当量当り、０．３〜１０．０モルである請求項１又は２に記載のカルボキシル基含有感光性樹脂。Addition rate of the alkylene oxide (b) for the phenolic novolak resin (a) is a phenolic hydroxyl group per equivalent of the phenolic novolak resin (a), according to claim 1 or 2 is 0.3 to 10.0 mol Carboxyl group-containing photosensitive resin. （Ａ）ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られるカルボキシル基含有感光性樹脂、（Ｃ）光重合開始剤、及び（Ｄ）エポキシ樹脂を含有することを特徴とするアルカリ現像可能な光硬化性・熱硬化性組成物。(A) A reaction product (c) of a novolak type phenol resin (a) and an alkylene oxide (b) is reacted with acrylic acid and / or methacrylic acid (d), and the reaction product (e) Photocurability capable of alkali development, comprising a carboxyl group-containing photosensitive resin obtained by reacting with a basic acid anhydride (f), (C) a photopolymerization initiator, and (D) an epoxy resin. -Thermosetting composition. （Ａ）ノボラック型フェノール樹脂（ａ）とアルキレンオキシド（ｂ）との反応生成物（ｃ）にアクリル酸及び／又はメタクリル酸（ｄ）を反応させ、得られた反応生成物（ｅ）と多塩基酸無水物（ｆ）とを反応させて得られるカルボキシル基含有感光性樹脂、（Ｂ）感光性（メタ）アクリレート化合物、（Ｃ）光重合開始剤、及び（Ｄ）エポキシ樹脂を含有することを特徴とするアルカリ現像可能な光硬化性・熱硬化性組成物。(A) A reaction product (c) of a novolak type phenol resin (a) and an alkylene oxide (b) is reacted with acrylic acid and / or methacrylic acid (d), and the reaction product (e) A carboxyl group-containing photosensitive resin obtained by reacting with the basic acid anhydride (f), (B) a photosensitive (meth) acrylate compound, (C) a photopolymerization initiator, and (D) an epoxy resin. A photocurable and thermosetting composition capable of alkali development. さらに（Ｅ）有機溶剤を含有する請求項４又は５に記載の光硬化性・熱硬化性組成物。Furthermore, (E) The photocurable and thermosetting composition of Claim 4 or 5 containing the organic solvent. さらに（Ｆ）硬化触媒を含有する請求項４乃至６のいずれか一項に記載の光硬化性・熱硬化性組成物。Furthermore, (F) The photocurable and thermosetting composition as described in any one of Claims 4 thru | or 6 containing a curing catalyst. 前記カルボキシル基含有感光性樹脂（Ａ）１００質量部（固形分として）に対して、０. ５〜２５質量部の割合の光重合開始剤（Ｃ）、及び１０〜７０質量部の割合のエポキシ樹脂（Ｄ）を含有する請求項４に記載の光硬化性・熱硬化性組成物。The photopolymerization initiator (C) in a proportion of 0.5 to 25 parts by mass and the epoxy in a proportion of 10 to 70 parts by mass with respect to 100 parts by mass (as a solid content) of the carboxyl group-containing photosensitive resin (A). The photocurable / thermosetting composition according to claim 4 containing a resin (D). 前記カルボキシル基含有感光性樹脂（Ａ）１００質量部（固形分として）に対して、５０質量部以下の割合の感光性（メタ）アクリレート化合物（Ｂ）、０. ５〜２５質量部の割合の光重合開始剤（Ｃ）、及び１０〜７０質量部の割合のエポキシ樹脂（Ｄ）を含有する請求項５に記載の光硬化性・熱硬化性組成物。50 parts by mass or less of the photosensitive (meth) acrylate compound (B) with respect to 100 parts by mass (as a solid content) of the carboxyl group-containing photosensitive resin (A), and a ratio of 0.5 to 25 parts by mass. The photocurable / thermosetting composition according to claim 5 , comprising a photopolymerization initiator (C) and an epoxy resin (D) in a proportion of 10 to 70 parts by mass. 前記カルボキシル基含有感光性樹脂（Ａ）１００質量部（固形分として）に対して、０．１〜２０質量部の割合の硬化触媒（Ｆ）を含有する請求項７に記載の光硬化性・熱硬化性組成物。The photocuring property according to claim 7 , comprising a curing catalyst (F) in a proportion of 0.1 to 20 parts by mass with respect to 100 parts by mass (as a solid content) of the carboxyl group-containing photosensitive resin (A). Thermosetting composition. さらに無機フィラーを、前記カルボキシル基含有感光性樹脂（Ａ）１００質量部（固形分として）に対して１０〜３００質量部の割合で含有する請求項４乃至１０のいずれか一項に記載の光硬化性・熱硬化性組成物。Furthermore, the light as described in any one of Claims 4 thru | or 10 which contains an inorganic filler in the ratio of 10-300 mass parts with respect to 100 mass parts (as solid content) of the said carboxyl group-containing photosensitive resin (A). Curable and thermosetting composition. さらに着色剤、熱重合禁止剤、増粘剤、消泡剤、レベリング剤及びシランカップリング剤よりなる群から選ばれる少なくとも１種の化合物を含有する請求項４乃至１１のいずれか一項に記載の光硬化性・熱硬化性組成物。Furthermore coloring agents, thermal polymerization inhibitors, thickeners, antifoaming agents, according to any one of claims 4 to 11 containing at least one compound selected from the group consisting of a leveling agent and a silane coupling agent Photocurable and thermosetting composition. 請求項４乃至１２のいずれか一項に記載の光硬化性・熱硬化性組成物を活性エネルギー線照射及び加熱により硬化させて得られる硬化物。A cured product obtained by curing the photocurable / thermosetting composition according to any one of claims 4 to 12 by irradiation with active energy rays and heating.
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